Title of Invention

HERBICIDALLY ACTIVE 3-HYDROXY-4-ARYL-5-OXOPYRAZOLINE DERIVATIVE COMPOUNDS OF THE FORMULA 1

Abstract Compounds of formula (I), in which the subsituents are as defined in claim 1, are suitable for use as herbicides, in particular in combination with herbicide-antagonistically effective compounds.
Full Text

HERBICIDALLY ACTIVE 3-HYDROXY-4-ARYL-5-OXOPYRAZOLINE DERIVATIVES
The present invention relates to novel herbicidally active 3-hydroxy-4-aryl-5-oxopyrazoline derivatives, to processes for their preparation, to compositions which comprise these compounds and may additionally comprise safeners, and to the use of these compounds as herbicides for controlling weeds and grasses, in particular in crops of useful plants.
3-Hydroxy-4-aryl-5-oxopyrazoline derivates having herbicidal action are described, for 'Sample, in EP-A-0 508 126, WO 96/25395 and WO 96/21652 . We have now found novel 3-hydroxy-4-aryl-5-oxopyrazoline derivatives having herbicidal properties.


C1-C4haloalkyl where an alkylene ring, which together with the carbon atoms of the groups Z1, Z2 or Z3 contains 2 to 6 carbon atoms and may be interrupted by oxygen, may either be fused or spiro-linked to the carbon atoms of the groups Z1, Z2 or Z3, or where this alkylene ring bridges at least one ring atom of the groups Z1, Z2 or Z3; G is hydrogen, -C(X1)-R30, -C(X2)-X3-R31, -C(X4)-N(R32)-R33. -SOrR**, an alkali metal, alkaline earth metal, sulfonium or ammonium cation or -P(X5)(R35)-R36; Xi, X2) X3, X4 and X5 independently of one another are oxygen or sulfur; and R30, R3L R32, R33, R34, R35 and R^ independently of one another are hydrogen, C1-C5alkyl, CrC5haloalkyl, C2-C5alkenyl, C1-C5alkoxyalkyl, C3-C6cycloalkyl or phenyl, and R34 is additionally C2-C20alkenyl, C2-C20alkenyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or substituted heteroaryl, C2-C20alkynyl, C2-C20alkynyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or substituted heteroaryl, (CrC7)cycloalkyl, (C1-C7)cycloalkyl substituted by halogen, haloalkyl, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryl, heteroaryl substituted by halogen, haloalkyl, nitro, cyano, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloaikylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and salts and diastereomers of the compounds of the formula I.
In the above definitions, halogen is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. The alkyl groups in the definitions of the substituents are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, and the isomeric pentyls and hexyls. Suitable cycloalkyl substituents

contain 3 to 6 carbon atoms and are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. These may be mono- or polysubstituted by halogen, preferably by fluorine, chlorine or bromine. Alkenyl is to be understood as meaning, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethinyl, propargyl, but-2-in-1-yl, 2-methylbutin-2-yl or but-3-in-2-yl. Haloalkyl groups preferably have a chain length of 1 to 4 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl. Suitable haloalkenyls are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and 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 which are mono-, di- or trisubstituted by halogen, preference is given to those having a chain length of 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, and the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Alkylthio groups preferably have a chain length of 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Alkoxyalkyl groups preferably have 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.


The halogen, alkyl, cycloalkyl, alkoxy, alkylthio, alkylcarbonyl, alkylsulfonyl and (di)alkyiamino radicals which may be present in the radicals R34, in particular -SO2R34 (G), are derived from the corresponding radicals mentioned above. Preferred heterocyclyl radicals are those containing 1 or 2 heteroatoms, for example N, S or O. They are usually saturated. Heteroaryl radicals are customarily aromatic heterocycles which preferably contain 1 to 3 heteroatoms, such as N, S and O. Examples of suitable heterocycles and heteroaromatics are: pyrrolidine, piperidine, pyran, dioxane, azetidine, oxetan, pyridine, pyrimidine, triazine, thiazole, thiadiazole, imidazole, oxazole, isoxazole and pyrazine, furan, morpholine, piperazine, pyrazole, benzoxazole, benzothiazole, quinoxaline and quinoline. These heterocycles and heteroaromatics may also be substituted, for example by halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, cyano, thioalkyl, alkylamino or phenyl. The C2-C2oalkenyl and alkynyl groups R34 may be mono- or polyunsaturated. They preferably contain 2 to 12, in particular 2 to 6, carbon atoms. For illustration, suitable groups -SO2R34 are given in the example below:





The free valency on the left hand of the groups Zi, Z2 and Z3 is linked to the 1-position and the free valency on the right hand is linked to the 2-position of the pyrazoline ring.
Compounds of the formula I, in which an alkylene ring which, together with the carbon atoms of the groups Zi, Z2 and Z3 contains 2 to 6 carbon atoms may be fused or spiro-linked to the groups Zi, Z2 and Z3, have, for example, the following structure:

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

R4 and R5 together are in particular a group
-C.R6(R7)-O-C-R8(R9)-C-R10(Rii)-C-Ri2(Ri3)- (Zi),
-C-Ri4(Ri5)-C-Rie(Ri7)-0-C-Ri8(Ri9)-C-Rao(R2i)- (Z2), or
-C-R22(R23)-C-R24(R25)-C-R26(R27)-0-C-R28(R29)- (Z3); in which R6, R7» Re? R9> Rio. Rn. Ri2» R131 RM> Ri5i Rie> Ri7» R181 R191 R2o» R211 R22, R23> R24» R25i R26, R27, R28 and R29 independently of one another are hydrogen, halogen, d-C4alkyl or CrC4haloalkyl, where an alkylene ring which, together with the carbon atoms of the groups Zi, Z2 and Z3, contains 3 to 6 carbon atoms may be fused or spiro-linked to the groups Ztf Z2 and Z3.

Among the compounds of the formula I, preference is given to those in which G is hydrogen. In a particularly preferred group of compounds of the formula I, R4 and R5 together form a group Z2. Also of particular interest are compounds of the formula I in which R1f R2 and R3 independently of one another are halogen, CrC4alkyl, C2-C4alkenyl, C2-C4alkynyl or CrC6-alkoxy. Particular preference is given to compounds of the formula I in which R2 is halogen, methyl, ethyl or ethinyl, and to compounds of the formula I in which Ri and R3 independently of one another are methyl, ethyl, isopropyl, vinyl, allyl, ethinyl, methoxy, ethoxy, bromine or chlorine. Very particular preference is given to compounds of the formula I in which G is the group -C(Xi)-R3o or C(X2)-(X3)-R31 in which Xi, X2 and X3 are, in particular, oxygen, and R^ and R3i independently of one another are preferably CrC5alkyl. Preference is furthermore given to compounds of the formula I in which Rx, R3i, R32, R^, R^, R3s and R^ independently of one another are hydrogen, d-C5alkyl or C1-C5haloalkyl.
Another preferred group of compounds of the formula I is is that where at least one ring atom of the groups Zi, Z2 or Z3 is bridged by an alkyiene ring which, together with the carbon atoms of the groups Z^t Z2 or Z3, contains 2 to 6 carbon atoms and may be interrupted by oxygen.
The invention also includes the salts which the compounds of the formula I can form with acids. Suitable acids for forming the acid addition salts are both organic and inorganic acids. Examples of such acids are hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid. The salts of the compounds of the formula I with acidic hydrogen also include alkali metal salts, for example sodium salts and potassium salts; alkaline earth metal salts, for example calcium salts and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or polysubstituted ammonium salts, and salts with other organic nitrogen bases. Correspondingly, suitable salt formers are alkali metal and alkaline earth metal hydroxides, in particular the hydroxides of lithium, sodium, potassium, magnesium or calcium, where those of sodium or potassium are particularly important.
Examples of amines which are suitable for forming ammonium salts are both ammonia and primary, secondary and tertiary CrCi8alkylamines, CrC4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine,

octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, 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-butylethanolamine, allylamine, n-butenyt-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-aminef n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, 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, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o, m, p-toluidines, phenylenediamines, benzidines, naphthylamines and o, m, p-chloroanilines; but in particular triethylamine, isopropylamine and diisopropylamine.
In the processes described in this application, unless chiral starting materials are employed, the unsymmetrically substituted compounds of the formula I are generally obtained as racemates. The stereoisomers can then be separated by known methods, such as fractional crystallization after salt formation with optically pure bases, acids or metal complexes, or else by chromatographic processes such as high pressure liquid chromatography (HPLC) on acetylcellulose, owing to their physicochemical properties. In the present invention, the active compounds of the formula I are to be understood as meaning both the enriched and optically pure forms of the stereoisomers in question, and the racemates or diastereomers. Unless specific reference is made to the individual optical isomers, the given formula is to be understood as meaning those racemic mixtures which are formed in the preparation process mentioned. If an aliphatic C=C double bond is present, geometrical isomerism may additionally occur.
Also depending on the type of the substituents, the compounds of the formula I may be present as geometrical and/or optical isomers and isomer mixtures, and also as tautomers and mixtures of tautomers. These compounds of the formula I likewise form part of the subject-matter of the present invention. The compounds of the formula I in which the group G is hydrogen may, for example, be present in the following tautomer equilibriums:


If G is different from hydrogen and Z is the group Zi or Z3, or if G is different from hydrogen and Z2is unsymmetrically substituted, fused or spiro-linked, the compound of the formula I may be present as an isomer of the formula Id
9
Processes for preparing compounds which, with respect to the meaning of the substituents R4 and R5, are different from the compounds of the formula I according to the present invention are, for example, described in WO 96/21652. The compounds of the formula I according to the present invention can be prepared by methods similar to the processes described in WO 96/21652. The compounds of the formula II


• ■ ■
in which R1,R2l R3, R4 and R5 are as defined under formula I and which are employed as starting materials for such processes can be prepared, for example, by reacting a compound of the formula III

in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 are as defined under formula I in an inert organic solvent, if appropriate in the presence of a base, with a compound of the formula IV or IVa

in which R4 and R5 are as defined under formula I. Other preparation processes for compounds of the formula II are described, for example, in WO 92/16510 .
The compounds of the formula III are either known, or they can be prepared similarly to known processes. Processes for preparing compounds of the formula III and their reaction with hydrazines are described, for example, in WO 97/02243 . Compounds of the formula III in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 are as defined under formula I can be prepared by methods known to the person skilled in the art. For example, compounds of the formula III in which R is C1-C6alkyl, C1-C6haloalkyl, preferably methyl, ethyl or trichloroethyl, and R1, R2 and R3 independently of one

another are C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl can be prepared by the process of cross-coupling according to Stille (J.K. Stille, Angew. Chem. 1986. 98, 504-519), Sonogashira (K. Sonogashira et al., Tetrahedron Lett. 1975. 4467-4470), Suzuki (N. Miyaura, A. Suzuki, Chem. Rev. 1995. 95, 2457-2483) or Heck (R.F. Heck, Org. React. 1982. 27, 345-390), with or without subsequent hydrogenation. This procedure is illustrated by the following reaction scheme:

The compounds of the formulae IV and IVa are either known, or they can be prepared by known processes. Processes for preparing compounds of the formula IV are described, for example, in WO 95/00521. These compounds can be prepared, for example, by heating a compound of the formula V
in which R42 is hydrogen, CrC4alkyl, CrC6alkoxy, Ci-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5 are as defined under formula I in the presence of a base or an acid in an inert solvent. Compounds of the formula V in which R42 is hydrogen, CrC4alkyl, CrC6alkoxy, d-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy and R4 and R5are as defined under formula I can be prepared, for example, by reacting a compound of the formula VI


in which R42 is hydrogen, C1-C4alkyl, C1-C6alkoxy, C1-C6haloalkoxy, benzyloxy, preferably hydrogen, methyl, methoxy, ethoxy, trichloroethoxy, tert-butoxy or benzyloxy in the presence of a base and an inert solvent with a compound of the formula VII

in which Y is halogen, alkyl/aryl sulfonates -OSO2R43, preferably bromine, chlorine, iodine, mesylate (R43 = CH3), triflate (R43 = CF3) or tosylate (R43 = p-tolyl) and Z1, Z2andZ3are as defined under formula I. In the formula VII, the free valencies of the groups Zi,Z2andZ3are in each case attached to the group Y. Compounds of the formula VI and VII are known, or they can be prepared by methods known to the person skilled in the art.
Compounds of the formula IV in which R4 and R5 together are a group Z2
-C-Ri4(Ri5)-C-R16(Ri7)-0-C-Rl8(Ri9)-C-R2o(R2i)- (Z2), in which R14, R15, Rie, R17, R18, R19, R20 and R2i are hydrogen can be prepared, for example, according to the following reaction scheme:

Compounds of the formula I in which R4 and R5 are a group Zn or Z3 can be prepared using the methods of the synthesis examples given above. Thus, the compounds of the formula III can, for example, be reacted with a hydrazine alkanol of the formula IV(b)


(here, R6-Ri3 and R22-R29 are hydrogen) to give the compounds of the formula IVc

followed by a cyclization, for example with formaldehyde, to give the end products of the formula le

The compound of the formula le in which R1 and R3 are ethyl and R2 is methyl has a melting point of 186-191 °C (decomp.). Similarly, it is also possible to prepare compounds of the formula I in which the substituents R6-R13 and R22-R29 are different from hydrogen and, independently of one another, have one of the meanings mentioned for them above.
The end products of the formula I can be isolated in a customary manner by concentration and/or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, alkanes, aromatic hydrocarbons or chlorinated hydrocarbons, or by chromatography. Salts of compounds of the formula I can be prepared in a manner known per se. Such preparation methods are described, for example, in WO 96/21652.
The compounds of the formula I or compositions comprising them can be used according to the invention by all the application methods customary in agriculture, for example pre-emergence application, postemergence application and seed dressing, and various methods and techniques, for example controlled release of active compounds. To this end, the active compound is absorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and dried. If appropriate, a coating which allows the active compound to be released in metered form over a certain period of time can additionally be applied (coated granules).

The compounds of the formula I can be employed as herbicides in unchanged form, i.e. as they are obtained in the synthesis, but they are preferably processed in a customary manner with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The methods of application, such as spraying, atomizing, dusting, wetting, scattering or watering, in the same way as the nature of the compositions, are chosen according to the required aims and the given circumstances.
The formulations, i.e. the compositions, formulations or preparations comprising the active compound of the formula I or at least one active compound of the formula I and as a rule one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can furthermore additionally be used during the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485 on page 6. Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, nonionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.
The surfactants conventionally used in the art of formulation and which can also be used to prepare the herbicidal compositions according to the invention are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch" [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81.
The efficacy of herbicidal and plant-growth-inhibiting compositions according to the invention containing a herbicidally effective amount of a compound of the formula I can be enhanced by addition of spray tank adjuvants.

These adjuvants may be, for example: nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with and without surfactants, vegetable oil derivatives with and without addition of surfactants, alkylated derivatives of oils of vegetable or mineral origin with and without surfactants, fish oils and other oils of animal nature and their alkyl derivatives with and without surfactants, natural higher fatty acids, preferably having 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids which contain an aromatic ring system and one or more carboxylic esters, and their alkyl derivatives, furthermore suspensions of polymers of vinyl acetate or copolymers of vinyl acetate/acrylic esters. Mixtures of individual adjuvants with one another and in combination with organic solvents may further increase the effect.
Suitable nonionic surfactants are, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, preferably those which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol preferably having 1 to 10 carbon atoms in the alkyl chain which preferably contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds generally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Other examples of nonionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Also suitable are fatty esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate.
Preferred anionic surfactants are, in particular, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids and their ethoxylated derivatives. The alkyl radicals usually contain 8 to 24 carbon atoms.

Preferred nonionic surfactants are known under the following trade names:
Polyoxyethylene cocoalkylamine (for example AMIET® 105 (Kao Co.)), polyoxyethylene oleylamine (for example AMIET® 415 (Kao Co.)), nonylphenolpolyethoxyethanols, polyoxyethylene stearylamine (for example AMIET® 320 (Kao Co.)), N-polyethoxyethylamines (for example GENAMIN® (Hoechst AG)), N,N,N',N'-tetra(polyethoxypolypropoxyethyl)ethylene diamines (for example TERRONIL®and TETRONIC® (BASF Wyandotte Corp.)), BRIJ® (Atlas Chemicals), ETHYLAN® CD and ETHYLAN® D (Diamond Shamrock), GENAPOL® C, GENAPOL® O, GENAPOL® S and GENAPOL® X080 (Hoechst AG), EMULGEN® 104P, EMULGEN® 109P and EMULGEN® 408 (Kao Co.); DISTY® 125 (Geronazzo), SOPROPHOR® CY 18 (Rhdne Poulenc S.A.); NONISOL® (Ciba-Geigy), MRYJ® (ICI); TWEEN® (ICI); EMULSOGEN® (Hoechst AG); AMIDOX® (Stephan Chemical Co.), ETHOMID® (Armak Co.); PLURONIC® (BASF Wyandotte Corp.), SOPROPHOR® 461P (Rhdne Poulenc S.A.), SOPROPHOR® 496/P (Rhone Poulenc S.A.), ANTAROX FM-63 (Rhone Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (Osi-Specialities).
The cationic surfactants are primarily quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower nonhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The oils used are either of mineral or natural origin. The natural oils may additionally be of animal or vegetable origin. In the case of animal oils, preference is given, in particular, to derivatives of beef tallow, but fish oils (for example sardine oil) and derivatives thereof are also used. Vegetable oils are mainly seed oils of various origin. Examples of particularly preferred vegetable oils which may be mentioned are coconut, rapeseed or sunflower oils and derivatives thereof.
Surfactants, oils, in particlar vegetable oils, derivatives thereof such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and higher fatty acids which are customary in formulation and adjuvant technique and which can also be employed in the compositions according to the invention and spray tank solutions thereof are described, inter

alia, in "Mc CutcheorVs Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1998, Stache, HM "Tensid-Taschenbuch" [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, "A Compendium of Herbicide Adjuvants", Southern Illinois Univ., 1998, L. Thomson Harvey, "A Guide to Agricultural Spray Adjuvants Used in the United States", Thomson PubnsM 1992.
The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are rather preferred as commercial goods, the end user as a rule uses dilute compositions. The compositions can also comprise further additives, such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active compounds.
The herbicidally active compounds of the formula I are as a rule applied to the plants or their habitat, at application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired effect can be determined by tests. It depends on the nature of the effect, the development stage of the crop plant and the weed and on the application (location, time, process) and can, as a function of these parameters, vary within wide ranges.
The compounds of the formula I have herbicidal and growth-inhibiting properties, owing to which they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantings, rapeseed, maize and rice, very particularly in maize and cereals, and for the non-selective control of weeds. Crops include those which have been rendered tolerant towards herbicides or herbicide classes by conventional breeding methods or genetical engineering methods. The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Agrostis, Digitaria, Avena, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola, Matricharia, Papaver and Veronica. The herbicidal composition according to the

invention is particularly suitable for controlling Alopecurus, Avena, Agrostis, Setaria, Phalaris, Lolium, Panicum, Echinochloa, Brachiaria and Digitaria.
Surprisingly, it has been found that specific safeners known from US-A-5 041 157, US-A-5-541 148, US-A-5 006 656, EP-A-0 094 349, EP-A-0 551 650, EP-A-0 268 554, EP-A-0 375 061, EP-A-0 174 562, EP-A-492 366, WO 91/7874, WO 94/987, DE-A-19 612 943, WO 96/29870, WO 98/13361, WO 98/39297, WO 98/27049, EP 716 073, EP 613 618, US-A-5 597 776 and EP-A-430 004 are suitable for mixing with the herbicidal composition according to the invention. Consequently, the present invention also relates to a selective herbicidal composition for controlling grasses and weeds in crops of useful plants, in particular in crops of maize and cereals, said composition comprising a herbicide of the formula I and a safener (antidote) and which protects the useful plants, but not the weeds, against the phytotoxic effect of the herbicide, and to the use of this composition for controlling weeds in crops of useful plants.
According to the invention, a selective-herbicidal composition is therefore proposed which, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, comprises, as active compound, a mixture of
a) a herbicidally effective amount of a compound of the formula I

in which Ri, R2, R3, R4, R5 and G are as defined above, and
b) a herbicide-antagonistically effective amount of either a compound of the formula X


in which R37 is hydrogen, C1-C8alkyl or C1-C6alkoxy- or C3-C6alkenyloxy-substituted C1-C8alkyl; and X6 is hydrogen or chlorine; or a compound of the formula XI

in which
E is nitrogen or methine;
R38 is -CCI3, phenyl or halogen-substituted phenyl;
R39 and R40 independently of one another are hydrogen or halogen; and
R41 is CrC4alkyl; or a compound of the formula XII

in which R44 and R45 independently of one another are hydrogen or halogen and R46. R47 and R48 independently of one another are C1-C4alkyl, or a compound of the formula XIII







in which R56 and R57 independently of one another are C1-C6alkyl or C2-C6alkenyl; or R56 and
pR«
R57 together are ; R58 and R59 independently of one another are hydrogen
or C1-C6alkyl; or R56 and R57 together are

Reo and R6i independently of one another are C1-C4alkyl, or R60and R6i together are -(CH2)5-; R62 is hydrogen, CrC4alkyl or
or Rse and R57 together are
Re3i Rw. R65i R66. R$7» R68» R69> R701 R?i, R721 R73» R74> R751 R761 R77 and R78 independently of one another are hydrogen or CrC4alkyl;
or a compound of the formula XV


in which Rso is hydrogen or chlorine and R79 is cyano or trifluoromethyl, or a compound of the formula XVI

in which R8i is hydrogen or methyl,


a) at least one of the ring members U, V, Wi or Z4 is carbonyl, and a ring member which is
C adjacent to this or these ring members is the group
, this group being present only once; and
b) two adjacent ring members U and V, V and W1 and Wt and Z4 may not simultaneously be
oxygen;
R95 and R96 independently of one another are hydrogen or C1C8alkyl; or
R95 and Rge together form a C2-C6alkylene group;
A, is R99-Y1- or -NR97R98;
X2 is oxygen or -S(0)s;
Yi is oxygen or sulfur;
R99 is hydrogen, C1-C8alkyl, C1-C8haloalkylf d-dalkoxy-C1-C8alkyl, C3-C6alkenyloxy-C1-
C8alkyl or phenyl-C1-C8alkyl, where the phenyl ring may be substituted by halogen, d-
C4alkyl, trifluoromethyl, methoxy or methyl-S(0)5-, C3-C6alkenylt C3-C6haloalkenyl, phenyl-
C3-C6alkenyl, d-C6alkynyl, phenyl-C3-C6alkynyl, oxetanyl, furyl or tetrahydrofuryl;
R85 is hydrogen or d-dalkyl;
R86is hydrogen, C1-C4alkyl or d-dalkylcarbonyl;
R87 is hydrogen or CrC4alkyl; or
Rse and R87 together form a C4- or C5alkylene group;
R88. RB9I R90 and R91 independently of one another are hydrogen orC1-C4alkyl; or R^
together with R89 or R90 together with R91 independently of one another are C4- or C5-
alkylene, where a carbon atom may be replaced by oxygen or sulfur, or one or two carbon
atoms may be replaced by -NR100-;
R92, R100 and R93 independently of one another are hydrogen or C1-C8alkyl; or
R92 and R93 together are C2-C6alkylene;
Rw is hydrogen or C1-C8alkyl;
R97 is hydrogen, C1-C8alkyl, phenyl, phenyl-C1-C8alkyl, where the phenyl rings may be
substituted by fluorine, chlorine, bromine, nitro, cyano, -OCH3, d-C4alkyl or CH3S02-f Cr
C4alkoxy-d-C8alkyl, C3-C6alkenyl or C3-C6alkynyl;
R98 is hydrogen, C1-C8alkyl, C3-C6alkenyl or C3-C6alkynyl; or

R97 and Rgs together are C4- or C5-alkylene, where a carbon atom may be replaced by
oxygen or sulfur, or one or two carbon atoms may be replaced by -NR10r;
R101 is hydrogen or d-C4alkyl;
r is 0 or 1; and
s is 0,1 or 2, or a compound of the formula XVIII

in which R103 is hydrogen, CrC6alkyl, C3-C6cycloalkyl, C3-C6alkenyl or C3-C6alkynyl; and R104,
R105 and R106 independently of one another are hydrogen, Ci-C6alkyl, C3-C6cycloalkyl or Cr
C6alkoxy, with the proviso that one of the substituents R104l R105 and Rioe is different from
hydrogen;
a compound of the formula XIX

in which Z5 is N or CH, n, in the case where Z5 is N, is 0,1,2 or 3 and, in the case where Z5 is CH, is 0,1,2, 3 or 4, R10? is halogen, CrC4alkyl, d-dhaloalkyl, d-dalkoxy, d-C4haloalkoxy, nitro, d-C4alky!thio, Ci-C4alkylsulfonyl, CrC4alkoxycarbonyl or unsubstituted or substituted phenyl or phenoxy, R10a is hydrogen or CrC4alkyl, R109is hydrogen, CrC4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C2-C6haloalkynyl, Ci-C4alkylthio-Ci-C4alkyl, Crdalkylsulfonyl-d-dalkyl, CrC4alkoxy-Cr C4alkyl, CrC4alkenyloxy-CrC4alkyl or CrC4alkynyloxy-CrC4alkyl; a compound of the formula XX


in which Zeis O or N-R110 and R110 is a group of the formula
in which Rm and R112 independently of one another are cyano, hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, unsubstituted or substituted phenyl or heteroaryl;
a compound of the formula XXI
in which Z7 is O, S, S=0, S02 or CH2, R113 and Rl14 independently of one another are hydrogen, halogen or Ci-C4alkyl, W2 and W3 independently of one another are CH2COORu5, COOR115 or together are a group of the formula -(CH2)C(0)-0-C(0)-(CH2)-, and R116 is hydrogen, Ci-C4alkyl, C2-C4alkenyl, CrC6alkynyl, C3-C6cycloalkyl, Ci-C4haloalkyl, a metal cation or an ammonium cation; a compound of the formula XXII

in which R119 and R120 independently of one another are hydrogen, halogen or Cr C4haloalkyl, R121 is hydrogen, d-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, CrC4haloalkyl, C3-C6cycloalkyl, a metal cation or an ammonium cation, Zeis N, CH, C-F or C-CI and W4 is a group of the formula


in which R122 and R123 independently of one another are hydrogen or d-C4alkyl and R124 and R125 independently of one another are hydrogen or CrC4alkyl; a compound of the formula XXIII

in which Ri26 is hydrogen, cyano, halogen, CrC4alkyl, C3-C6cycloalkyl, d-C4alkoxy, d-
C4alkoxycarbonyl, Ci-C4alkylthiocarbonyl, -NH-Ri28i -C(0)NH-Ri28, unsubstituted or
substituted aryl or heteroaryl,
R127is hydrogen, cyano, nitro, halogen, Ci-C4alkyl, Ci-C4haloalkyl, d-C4alkoxy, d-
C4thioalkyl, CrC4haloalkyl, -NH-R128, -C(0)NH-R128, unsubstituted or substituted aryl,
heteroaryl, and Ri28is CrC4alkyl, CrC4haloalkyl, C3-C4alkenyl, C3-C4alkynyl, C3-C4cycloalkyl,
unsubstituted or substituted aryl or heteroaryl, formyl, CrC4-alkylcarbonyl, d-C4-
alkylsulfonyl;
a compound of the formula XXIV

in which Ri29 and R130 independently of one another are hydrogen, Ci-C4alkyl, d-C4haloalkyl, CrC4alkoxy, mono-CrC8- or di-Crdalkylamino, C3-C6cycloalkyl, CrC4thioalkyl, phenyl or heteroaryl, R131 has the meaning of Ri29 and is additionally OH, NH2, halogen, di-CrC4aminoalkyl, CrC4alkylthio, CrC4alkylsulfonyl or Ci-C4alkoxycarbonyl, R132 has the meaning of Ri29 and is additionally cyano, nitro, carboxyl, Ci-C4alkoxycarbonyl, di-Cr C4aminoalkyl, CrC4alkylthio, CrC4alkylsulfonyl, S02-OH,
iso-Ci-C4aminoalkylsulfonyl or Ct-C4alkoxysulfonyl, R133 has the meaning of R129 and is additionally OH, NH2, halogen, di-CrC4aminoalkyl, pyrrolidin-1-yl, piperidin-1-yl,

morpholin-1-yI, CrC4alkylthio, CrC4alkylsulfonyl, d-C4alkoxycarbonyl, phenoxy, naphtoxy, phenylamino, benzoyloxy or phenylsulfonyloxy; or a compound of the formula XXV

in which R^is hydrogen, C4alkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4alkynyl or CrC4alkoxy-CrC4alkyl, R135 is hydrogen, halogen, CrC4alkyl, CrC4haloalkyl or d-C4alkoxy and Ri3eis hydrogen, halogen, CrC4alkyl, CrC4haloalkyl or d-C4alkoxy, with the proviso that R135 and R136 are not simultaneously hydrogen.
The selective-herbicidal composition according to the invention preferably comprises, as herbicide-antagonistically effective amount, either a compound of the formula X

in which R37 is hydrogen, CrC8alkyl or CrC6alkoxy- or C3-C6alkenyloxy-substituted d-C8alkyl; and X6 is hydrogen or chlorine; or a compound of the formula XI

in which
E is nitrogen or methine; R38 is -CCI3, phenyl or halogen-substituted phenyl;

R39 and R40 independently of one another are hydrogen or halogen; and R41 is CrC4alkyl; or a compound of the formula XII

in which R44 and R45 independently of one another are hydrogen or halogen and R46, R47 and R48 independently of one another are CrC4alkyl.
The abovementioned preferences for the compounds of the formula I also apply to mixtures of the compounds of the formula I with safeners of the formulae X to XVIII. Preferred compositions according to the invention comprise a safener selected from the group consisting of the formula Xa























The invention also relates to a method for the selective control of weeds in crops of useful plants which comprises treating the useful plants, their seeds or seedlings or the area on which they are cultivated jointly or separately with a herbicidally effective amount of the herbicide of the formula I and a herbicide-antagonistically effective amount of the safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII.
Crop plants which can be protected against the damaging effect of the abovementioned herbicides by the safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII are, in particular, cereals, cotton, soya, sugarbeet, sugarcane, plantings, rapeseed, maize and rice, very particularly maize and cereals. Crops are to be understood as including those which have been rendered tolerant towards herbicides or classes of herbicides by conventional breeding methods or genetical engineering methods.
The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, for example the monocotyledonous weeds Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria Brachiaria, Echinochloa, Panicum, Sorghum halTbic, Rottboellia, Cyperus, Brachiaria, Scirpus, Monochoria, Sagittaria, and Stellaria and the dicotyledonous weeds Sinapis, Chenopodium, Galium, Viola, Veronica, Matricaria, Papaver, Solanum, Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.

Areas under cultivation are the areas on which the crop plants are already growing, or on which the seeds of these crop plants have been sown, and also the soils which are intended to be cultivated with these crop plants.
Depending on the intended use, a safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII can be employed for pretreating the seeds of the crop plant (dressing of the seeds or the seedlings), or it can be worked into the soil before or after seeding. However, it can also be applied on its own or together with the herbicide after the plants have emerged. Thus, the treatment of the plants or the seeds with the safener can, in principle, be carried out independently of when the herbicide is applied. However, the plant can also be treated by simultaneous application of herbicide and safener (for example as tank mix). The application rate of safener to herbicide to be applied depends essentially on the type of application. In a field treatment which is carried out either by using a tank mix of a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener is as a rule from 100:1 to 1:10, preferably from 20:1 to 1:1. As a rule, 0.001 to 1.0 kg of safener/ha, preferably 0.001 to 0.25 kg of safener/ha are applied in the field treatment.
The application rates of herbicide are as a rule between 0.001 and 2 kg/ha, but preferably v between 0.005 to 0.5 kg/ha.
The compositions according to the invention are suitable for all application methods which are customary in agriculture, for example preemergence application, postemergence application and seed dressing.
For seed dressing, generally 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form while swelling the seeds shortly before seeding, it is advantageous to employ safener solutions which comprise the active compound in a concentration of from 1 to 10000, preferably from 100 to 1000, ppm.
For application, the safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII or combinations of these safeners with the herbicides of the formula I are advantageously processed together with auxiliaries conventionally used in the art of formulation, for example to give emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.

Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The formulations are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with liquid or solid formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can furthermore additionally be used during preparation of the formulations. Solvents and solid carriers which are suitable for this purpose are mentioned, for example, in WO 97/34485 on page 6.
Suitable surface-active compounds are, depending on the nature of the active compound of the formula I to be formulated, nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, nonionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8. The surfactants conventionally used in the art of formulation and which can also be used in the preparation of the herbicidal compositions according to the invention are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, HM "Tensid-Taschenbuch" [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81.
The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of the active compound mixture of the compound of the formula I with the compounds of the formulae X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII, 1 to 99.9% by weight of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are usually preferred as commercial goods, the end user as a rule uses dilute compositions.
The compositions can also comprise further additives, such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active substances. For using safeners of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII or compositions comprising them to protect crop plants against damaging effects of herbicides of the formula I, various methods and techniques are suitable, for example the following:
\) Seed dressing
a) Dressing the seeds with an active compound of the formula X, XI, XII, XIII, XIV, XV, XVI,
XVII or XVIII formulated as a wettable powder by shaking in a vessel until even distribution

on the surface of the seeds is achieved (dry dressing). Here, approximately 1 to 500 g of active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII (4 g to 2 kg of wettable powder) are employed per 100 kg of seed.
b) Dressing the seeds using an emulsion concentrate of the active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII according to method a) (wet dressing).
c) Dressing by dipping the seeds for 1 to 72 hours into a liquor containing 1-1000 ppm of active compound of the formula X, XI, XII, Xtll, XIV, XV, XVI, XVII or XVIII, with or without subsequent drying of the seeds (dip dressing).
Seed dressing or the treatment of the germinated seedling are the naturally preferred application methods, since the treatment with active compound is completely directed at the target culture. As a rule, 1 to 1000 g of antidote, preferably 5 to 250 g of antidote, are employed per 100 kg of seed, but, depending on the method, which also permits the addition of other active compounds or micronutrients, it is possible to deviate above or below the stated limit concentrations (repeat dressing).
ii) Application as tank mix
A liquid preparation of a mixture of antidote and herbicide (mutual ratio between 10:1 and 1:100) is employed, the application rate of herbicide being from 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after seeding.
iii) Application in the seed farrow
The active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII is applied into the open seeded seed farrow as an emulsion concentrate, a wettable powder or as granules. After the seed farrow has been covered, the herbicide is applied in a customary manner by the pre-emergence method.
iv) Controlled release of active compound
The active compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII is absorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and dried. If appropriate, a coating which allows the active compound to be released in metered form over a certain period of time can be applied (coated granules).
The efficacy of herbicidal and plant-growth-inhibiting compositions according to the invention comprising a herbicidally effective amount of a compound of the formula I and a herbicide-

antagonistically effective amount of a compound of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII can be increased by addition of spray tank adjuvants.
These adjuvants may be, for example, nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with or without surfactants, vegetable oil derivatives with or without addition of surfactants, alkylated derivatives of oils of vegetable or mineral origin with or without surfactants, fish oils and other oils of animal nature and their alkyl derivatives with or without surfactants, natural higher fatty acids, preferably having 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids which contain an aromatic ring system and one or more carboxylic esters, and their alkyl derivatives, furthermore suspensions of polymers of vinyl acetate or copolymers of vinyl acetate/acrylic esters. Mixtures of individual adjuvants with one another and in combination with organic solvents may further increase the effect.
Suitable nonionic surfactants are, for example, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, preferably those which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol preferably having 1 to 10 carbon atoms in the alkyl chain which preferably contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds generally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Other examples of nonionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Also suitable are fatty esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate.

Preferred anionic surfactants are, in particular, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylated phosphoric acids and their ethoxylated derivatives. The alkyl radicals usually contain 8 to 24 carbon atoms.
Preferred nonionic surfactants are known under the following trade names:
Polyoxyethylene cocoalkylamine (for example AMIET® 105 (Kao Co.)), polyoxyethylene oleylamine (for example AMIET® 415 (Kao Co.)), nonylphenolpolyethoxyethanols, polyoxyethylene stearylamine (for example AMIET® 320 (Kao Co.)), N-polyethoxyethylamines (for example GENAMIN® (Hoechst AG)), N,N,N',N'-tetra(polyethoxypolypropoxyethyl)ethylene diamines (for example TERRONIL®and TETRONIC® (BASF Wyandotte Corp.)), BRIJ® (Atlas Chemicals), ETHYLAN® CD and ETHYLAN® D (Diamond Shamrock), GENAPOL® C, GENAPOL® O, GENAPOL® S and GENAPOL® X080 (Hoechst AG), EMULGEN® 104P, EMULGEN® 109P and EMULGEN® 408 (Kao Co.); DISTY® 125 (Geronazzo), SOPROPHOR® CY 18 (Rhone Poulenc S.A.); NONISOL® (Ciba-Geigy), MRYJ® (ICI); TWEEN® (ICI); EMULSOGEN® (Hoechst AG); AMIDOX® (Stephan Chemical Co.), ETHOMID® (Armak Co.); PLURONIC® (BASF Wyandotte Corp.), SOPROPHOR® 461P (Rhone Poulenc S.A.), SOPROPHOR® 496/P (Rhone Poulenc S.A.), ANTAROX FM-63 (Rh6ne Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET408, SILWET L-7607N (Osi-Specialities).
The cationic surfactants are primarily quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower nonhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The oils used are either of mineral or natural origin. The natural oils may additionally be of animal or vegetable origin. In the case of animal oils, preference is given, in particular, to derivatives of beef tallow, but fish oils (for example sardine oil) and derivatives thereof are also used. Vegetable oils are mainly seed oils of various origin. Examples of particularly

preferred vegetable oils which may be mentioned are coconut, rapeseed or sunflower oils and derivatives thereof.
Surfactants, oils, in particlar vegetable oils, derivatives thereof such as alkylated fatty acids and mixtures thereof, for example with preferably anionic surfactants such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulfonates and higher fatty acids which are customary in formulation and adjuvant technique and which can also be employed in the compositions according to the invention and spray tank solutions thereof are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1998, Stache, H., "Tensid-Taschenbuch" [Surfactant handbook], Carl Hanser Verlag, Munich/Vienna, 1990, M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, "A Compendium of Herbicide Adjuvants", Southern Illinois Univ., 1998, L. Thomson Harvey, "A Guide to Agricultural Spray Adjuvants Used in the United States", Thomson Pubns., 1992.
In particular, preferred formulations have the following compositions: (% = per cent by weight)
Emulsifiable concentrates:
active compound mixture: 1 to 90%, preferably 5 to 20%
surface-active agent: 1 to 30%, preferably 10 to 20%
liquid carrier: 5 to 94%, preferably 70 to 85%
Dusts:
active compound mixture: 0.1 to 10%, preferably 0.1 to 5%
solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates:
active compound mixture: 5 to 75%, preferably 10 to 50%
water: 94 to 24%, preferably 88 to 30%
surface-active agent: 1 to 40%, preferably 2 to 30%
Wettable powders:
active compound mixture: 0.5 to 90%, preferably 1 to 80%
surface-active agent: 0.5 to 20%, preferably 1 to 15%








The application is carried out as an aqueous suspension of the test substances, prepared from a 25% wettable powder (Example F3, b))f using 500 I of water/ha. 3 weeks after the application, the phytotoxic effect of the herbicide on the crop plants, for example maize and cereals, is evaluated using a percentage scale. 100% means that the test plant has died, 0% means no phytotoxic effect.
The results obtained in this test show that the damage to the crop plants caused by the herbicide of the formula I can be considerably reduced using the compounds of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII.
The same results are obtained when the mixtures are formulated in accordance with Examples F1, F2 and F4 to F8.
Biological Example 2: Safeninq of the compound no. 1.032
Under greenhouse conditions, the test plants are grown in plastic pots until they have reached the 4-leaf-stage. In this stage, both the herbicide on its own and the mixtures of the herbicide with the test substances to be tested as safeners are applied to the test plants. The application is carried out as an aqueous suspension of the test substances, prepared from an emulsion concentrate (EC 100; Example F1) of the herbicides and an emulsion concentrate (EC 100; Example F1) of the safeners (exceptions: the safeners no. 10.05 and 20.17, which are employed as a 25% wettable powder (Example F3, b)). 9 days after the application, the phytotoxic effect of the herbicide on summer wheat and durum wheat is evaluated using a percentage scale (100%: test plant has died; 0%: no phytotoxic effect).


Biological Example 3: Safeninq of the compound no. 1.025 Under greenhouse conditions, the test plants are grown in plastic pots until they have reached the 4-leaf-stage. In this stage, both the herbicide on its own and the mixtures of the herbicide with the test substances to be tested as safeners are applied to the test plants. The application is carried out as an aqueous suspension of the test substances, prepared from an emulsion concentrate (EC 100; Example F1) of the herbicides and an emulsion concentrate (EC 100; Example F1) of the safeners (exceptions: the safeners no. 10.05 and 20.17, which are employed as a 25% wettable powder (Example F3, b)). 11 days after the application, the phytotoxic effect of the herbicide on summer wheat and durum wheat is evaluated using a percentage scale (100%: test plant has died; 0%: no phytotoxic effect).


Biological Example 4: Safeninq of the compound no. 1.007
Under greenhouse conditions, the test plants are grown in plastic pots until they have reached the 4-leaf-stage. in this stage, both the herbicide on its own and the mixtures of the herbicide with the test substances to be tested as safeners are applied to the test plants. The application is carried out as an aqueous suspension of the test substances, prepared from an emulsion concentrate (EC 100; Example F1) of the herbicides and an emulsion concentrate (EC 100; Example F1) of the safeners (exceptions: the safeners no. 10.05 and 20.17, which are employed as a 25% wettable powder (Example F3, b)). 9 days after the application, the phytotoxic effect of the herbicide on summer wheat and durum wheat is evaluated using a percentage scale (100%: test plant has died; 0%: no phytotoxic effect).




Over a period of one hour, a solution of 177.6 g of methanesulfonyl chloride and 400 ml of diethyl ether is added dropwise to a solution of 80.6 g (0.76 mol) of diethylene glycol and 159.9 g (1.58 mol) of triethylamine in 1500 ml of diethyl ether which had been cooled to -10°C, and during the addition, the temperature is kept below 5°C. The mixture is stirred at a temperature of 0°C for 30 minutes, and cooling is then removed. After 2 hours, at a temperature of 20°C, 12 ml of triethylamine and 12 ml of methanesulfonyl chloride are added, and stirring is continued for another 4 hours. The resulting white suspension is subsequently transferred onto a suction filter, and the residue is washed twice with 300 ml of diethyl ether. The filter cake is taken up in 2000 ml of ethyl acetate, and the suspension is stirred at room temperature for 30 minutes and then filtered again. The resulting filtrate is concentrated and the residue is used for the next reaction without any further purification. 216.5 g of the desired crude product (1) are obtained in the form of white crystals.
Example H2:

(1) (2) (3)
A solution of 68.78 g (0.30 mol) of (2) in 140 ml of dimethylformamide is added dropwise for a period of 30 minutes to a suspension of 23.9 g (0.60 mol) of 60% sodium hydride in 500 ml of dimethylformamide which had been cooled to 5°C. Cooling is removed and the reaction mixture is stirred until it has reached a temperature of 20°C. The mixture is subsequently briefly heated to a temperature of from 30 to 40°C to bring the evolution of hydrogen to completion. After cooling to a temperature of from 0 to 5°C, a solution of 80 g (0.305 mol) of (1) in 160 ml of dimethylformamide is added dropwise over a period of 30 minutes, during

which the temperature is kept at from 0 to 5°C. Cooling is removed and the reaction mixture is stirred at room temperature for 3 hours and at approximately 40°C for 45 minutes and then added to a mixture of saturated ammonium chloride solution, ice and tert-butyl methyl ether. The phases are separated and the organic phase is subsequently washed with water (2x). The organic phase is dried with sodium sulfate and evaporated, and the residue is dried further at a temperature of 40°C and under reduced pressure, giving 92.2 g of (3) in the form of a slightly yellow oil. The crude product is employed for the next reaction without any further purification.
Example H3:

(3) (4)
160.5 ml of a 33% solution of hydrogen bromide in glacial acetic acid are added dropwise over a period of 30 minutes to a solution of 92.2 g (0.305 mol) of (3) in 1200 ml of diethyl ether which had been cooled to 0°C. Cooling is removed and the mixture is subsequently stirred at 20°C for 22 hours and then under reflux for 27 hours, the resulting white suspension is transferred onto a suction filter and washed with diethyl ether, and the filter residue is subsequently dried over P205 under reduced pressure at a temperature of from 50 to 60°C. The product (4) is obtained in a yield of 52.9 g in the form of a white solid.

(4) (5) (6)
71.8 g (0.71 mol) of triethylamine are added to a suspension of 40 g (0.15 mol) of (4) in 1000 ml of xylene, and the mixture is degassed (4 x vacuum/argon). The yellow suspension

is subsequently heated to a temperature of 60°C and stirred for 3 hours. 42.5 g (0.15 mol) of
(5) are then added, and the mixture is heated to a bath temperature of 150°C to distil off
excess triethylamine and the ethanol which is formed. After 3 hours, the reaction mixture is
cooled to a temperature of 40°C and added to 500 ml of an ice/water mixture. Using 100 ml
of aqueous 1N sodium hydroxide solution, the reaction mixture is made alkaline and the
aqueous phase (which contains the product) is washed twice with ethyl acetate. The organic
phase is reextracted twice using aqueous 1N sodium hydroxide solution, the aqueous
phases are combined, the remaining xylene is distilled off and the combined aquoeus
phases are adjusted to pH 2-3 using 4N HCI with cooling. The product which precipitates is
transferred onto a suction filter, the filter cake is washed with water and briefly with hexane
and is subsequently dried under reduced pressure at a temperature of 60°C over P205. This
gives 34.6 g of (6) as a slightly beige solid of melting point 242-244°C (decomp.).
Example H5:

A catalytic amount of 4-dimethylaminopyridine is added to a solution of 3 g (10.4 mmol) of
(6) and 1.6 g (15.8 mmol) of triethylamine in 100 ml of tetrahydrofuran which had been
cooled to a temperature of 0°C. 1.57 g (13.0 mmol) of pivaloyl chloride are subsequently
added dropwise. The mixture is stirred at a temperature of 0°C for 30 minutes, cooling is
removed, and the mixture is stirred for a further 60 minutes. The reaction mixture is
subsequently poured into saturated aqueous sodium chloride solution, and the organic
phase is separated off. The organic phase is dried over magnesium sulfate, filtered off and
concentrated. Chromatographic purification and recrystallization from diethyl ether gives
2.94 g of (7) of melting point 135-136°C.

Example H6: Preparation of

First 36.7 g (0.116 mol) of tributylvinylstannane and then 2 g of tetrakis(triphenylphosphine)palladium are added to a solution of 20 g of dimethyl 2-(2,6-dibromo-4-methyl-phenyl)malonate (52.6 mmol) in 400 ml of toluene (3 x degassed, vacuum/argon). The reaction mixture is then stirred at a temperature of from 90 to 95°C for 9 hours. Filtration through Hyflo and concentration on a rotary evaporator gives, after chromatographic purification, 15.3 g of (8) in the form of a yellow oil which is used for the next reaction without any further purification.

At a temperature of from 20 to 25°C, 15.2 g of the compound (8) obtained according to Example H6 are hydrogenated with hydrogen over a palladium catalyst (using carbon as carrier, 7 g of 5% Pd/C) in 160 ml of tetrahydrofuran. After the hydrogenation has ended, the product is filtered through Hyflo, and the resulting filtrate is concentrated on a rotary evaporator. This gives 13.7 g of (9) in the form of yellow crystals of melting point 47 - 49°C.


By the method of Preparation Example H4, but starting from 4.8 g (17.2 mmol) of the malonate (9), 4.56 g of the compound (10) are obtained as a solid of melting point 188-190°C.

A catalytic amount of 4-dimethylaminopyridine is added to a solution of 1 g (3.2 mmol) of (10) and 0.65 g (6.4 mmol) of triethylamine in 30 ml of tetrahydrofuran which had been cooled to a temperature of 0°C. 0.49 g (4.1 mmol) of pivaloyl chloride is subsequently added dropwise. The mixture is stirred at a temperature of 0°C for 10 minutes, cooling is removed, and stirring is then continued for a further 90 minutes. The reaction mixture is poured into saturated aqueous sodium chloride solution and diluted with tert-butyl methyl ether, and the organic phase is separated off. The organic phase is dried over magnesium sulfate, filtered off and concentrated. Chromatographic purification gives 1.07 g of (11) in the form of a white solid of melting point 122-123°C.


(12) (13)
67.8 g (0.59 mol) of methanesulfonyl chloride are added dropwise to a solution of 37.1 g (0.28 mol) of c/s-2,5-bis(hydroxymethyl)tetrahydrofuran (12) and 65.3 g (0.65 mol) of triethylamine in 400 ml of methylene chloride which had been cooled to 0-3°C, during which the temperature is kept below 7°C. The mixture is subsequently stirred at a temperature of 20°C overnight. The resulting white suspension is transferred onto a suction filter, the residue is washed with methylene chloride and the filtrate is concentrated. The residue is taken up in ethyl acetate, washed with water (2x) and with saturated aqueous sodium chloride solution (1x), dried (Na2S04) and concentrated. This gives 72.7 g of the dimesylate compound (13) as a crude oil which is employed for the next reaction without any further purification.
The starting material (12) is known from the literature: see, for example, K. Naemura et al., Tetrahedron Asymmetry 1993, 4, 911-918.

Example H11: By the method of Preparation Example H2, but starting from 21.0 g (0.53 mol) of 60% NaH, 58.4 g (0.25 mol) of (2) and 72.5 g (0.25 mol) of dimesylate (13) in a total of 840 ml of dimethylformamide, (14) is obtained as a crude brown oil. Chromatographic purification gives 53.7 g of the pure compound (14) as a white solid of melting point 81 - 83°C.


(15)
Example H12: (14)
By the method of Preparation Example H3, but starting from 53.5 g (0.16 mol) of (14) in 800 ml of diethyl ether and 90 ml of a 33% solution of hydrogen bromide in cone, acetic acid, 36.5 g of the bicyclic hydrazine (15) are obtained as a solid of melting point 262 - 264°C.
(15) '» ' (16)
By the method of Preparation Example H4, but starting from 0.105 mol of the malonate (9) and 30.4 g (0.105 mol) of the hydrazine (15), 29.7 g of the compound (16) are obtained as a solid of melting point 287°C.

By the method of Preparation Example H9, but starting from 1.1 g (3.2 mmol) of (16), 0.83 g of the pivaloyl ester (17) is obtained as a solid of melting point 141-143°C.



















































Compound No. 1.01

according to the present invention, and compound A

from the prior art (EP-A-0 508 126, compound no. 46 of Table 1).
Example B1: Herbicidal action before emergence of the plants (pre-emergence action) Monocotyledonous and dicotyledonous weeds are sown in standard soil in plastic pots. Immediately after sowing, the test substances are applied (5001 of water/ha) as an aqueous suspension (prepared using a 25% wettable powder (Example F3, b)) or as an emulsion (prepared using a 25% emulsion concentrate (Example F1, c)). The application rate is 500 g of active substance/ha. The test plants are subsequently grown under optimum conditions in a greenhouse. 3 weeks after the application, evaluation is carried out using a nine-level scale of ratings (1 = complete damage, 9 = no effect). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.
Test plants: Alopecurus (AIo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra).
Table B1: Pre-emergence action:


bxampie B2: Herbicidal action after emergence of the plants (post-emergence actionV. Monocotyledonous and dicotyledonous weeds are grown in standard soil in plastic pots under greenhouse conditions. The test substances are applied at the 3- to 6-leaf stage of the test plants. The test substances are applied (5001 of water/ha) as an aqueous suspension (prepared using a 25% wettable powder (Example F3, b)) or as an emulsion (prepared using a 25% emulsion concentrate (Example F1, c)) at an application rate of 500 g of active substance/ha. 3 weeks after the application, evaluation is carried out using a nine-level scale of ratings (1 = complete damage, 9 = no effect). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.
Test plants: Alopecurus (Alo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra).
Table B2: Post-emergence action:

Comparing the herbicidal action of the compound A of the prior art with the compound no. 1.01 of the present invention, it can be seen that the compound no. 1.01 surprisingly exhibits considerably better herbicidal action against all of the weeds tested, although this compound differs from the compound A only in that an alkylene group in the ring has been replaced by oxygen.
Example B3: Herbicidal action of compounds of the present invention before emergence of the plants (pre-emeraence action):
Monocotyledonous and dicotyledonous weeds are grown in standard soil in plastic pots. Directly after sowing, the test substances are applied (5001 of water/ha) as an aqueous suspension (prepared using a 25% wettable powder (Example F3, b)) or as an emulsion (prepared using a 25% emulsion concentrate (Example F1, c)). The application rate is 500 g of active substance/ha. The test plants are subsequently grown under optimum conditions in a greenhouse 3 weeks after the application, evaluation is carried out using a nine-level scale

of ratings (1 = complete damage, 9 = no effect). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.
Test plants: Avena (Ave), Lolium (Lol), Setaria (Set).
Table B3: Pre-emergence action:

The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8.
Example B4: Herbicidal action of compounds of the present invention after emergence of the plants (post-emergence action):
Monocotyledonous and dicotyledonous weeds are grown in standard soil in plastic pots under greenhouse conditions. The test substances are applied at the 3- to 6-leaf stage of the test plants. The test substances are applied (500 I of water/ha) as an aqueous suspension (prepared using a 25% wettable powder (Example F3, b)) or as an emulsion (prepared using a 25% emulsion concentrate (Example F1, c)) at an application rate of 250 g of active substance/ha. 3 weeks after the application, evaluation is carried out using a nine-level scale of ratings (1 = complete damage, 9 = no effect). Ratings of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal action.
Test plants: Avena (Ave), Lolium (Lol), Setaria (Set). Table B4: Post-emergence action:



The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8.




WE CLAIM :
1. A compound of the formula I

in which
R1, R2 and R3 independently of one another are halogen, nitro, cyano, C1-
C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C3-
C6cycloalkyl, halogen-substituted C3-C6cycloalkyl, C1-C6alkoxyalkyl, C1-
C6alkylthioalkyl, hydroxy 1, mercapto, C1 -C6alkoxy, C3-C6alkeny loxy, C3-
C6alkynyloxy, C1-C4alkylcarbonyl,C1-C4alkoxycarbonyl, C1-C4alkylthio, Cr
C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C 1-C4alkylamino or di(C 1 -C4-
alkyl)amino;

R22. R23, R24, R25, R26, R27, R28, and R29 independently of one another are hydrogen, halogen, C1-C4alkyl or C1-C4 haloalkyl where an alkylene ring, which together with the carbon atoms of the groups Zl5 Z2 or Z3 contains 2 to 6 carbon atoms and may be interrupted by oxygen, may either be fused or spiro-linked to the carbon atoms of the groups Zl5 Z2 or Z3, or where this alkylene ring bridges at least one ring atom of the groups Zb Z2 or Z3; G is hydrogen, -C(X1)-R30, -C(X2)-X3-R31, -C(X4)-N(R32)-R33, -S02-R34, an alkali metal, alkaline earth metal, sulfonium or ammonium cation or -P(X5)(R35)-R36;

Xb X2, X3, X4 and X5 independently of one another are oxygen or sulfur; and R30, R31, R32> R33, R34, R35 and R36 independently of one another are hydrogen, C1-C5alkyl, C1-C5haloalkyl, C2-C5alkenyl, C1-C5alkoxyalkyl, C3-C6cycloalkyl or phenyl, and
R34 is additionally C2-C20alkenyl, C2-C20alkenyl substituted by halogen,
alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl,
alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl,
alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy,
alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino,
dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl,
(C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl,
heteroaryl or substituted heteroaryl, C2-C2oalkynyl? C2-C2oalkynyl substituted
by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy,
thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl,
alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy,
alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkyl-alkylcarbonylamino, cyano, (C3-C7)cycloalkyl, (C3-C7)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or substituted heteroaryl, (C1 -C7)cycloalkyl, (C1 -C7)cycloalky 1 substituted by halogen, haloalkyl, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryl, heteroaryl substituted by halogen, haloalkyl, nitro, cyano, (C1-C6)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or trialkylsilyloxy, heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and salts and diastereomers of the compounds of the formula I.


6. A compound according to claim 1, wherein R1, R2 and R3 independently of one
another are halogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl or C1-c6alkoxy.
7. A compound according to claim 1, wherein R2 is halogen, methyl, ethyl or ethinyl.
8. A compound according to claim 1, wherein G is the group -C(X1)-R30 or C(X2)-(X3)-R31 in which Xu X2 and X3 are oxygen and R30 and R3] independently of one another are CrC5alkyl.
9. A compound according to claim 1, wherein R{ and R3 independently of one
another are methyl, ethyl, isopropyl, vinyl, allyl, ethinyl, methoxy, ethoxy,
bromine or chlorine.

10. A compound according to claim 1, wherein K30, K31, K32, K33, K34, K35 ana R36
independently of one another are hydrogen, C1-C5alkyl or C1-C5haloalkyl.
11. A herbicidal and plant-growth-inhibiting composition, which contains a
herbicidally effective amount of a compound of the formula I on an inert
carrier.
12. A method for controlling undesirable plant growth, wherein a herbicidally
effective amount of an active compound of the formula I or a composition
which contains this active compound is applied to the plants or their habitat.
13. A selective-herbicidal composition which comprises as active compound, in
addition to customary inert formulation auxiliaries, a mixture of
a) a herbicidally effective amount of a compound of the formula I
according to claim 1 and
b) a herbicide-antagonistically effective amount of either a compound of
the formula X

in which R37 is hydrogen, C1-C8alkyl or C1-C6alkoxy- or C3-C6alkenyloxy-substituted C1-C8alkyl; and X6 is hydrogen or chlorine; or a compound of the formula XI


in which
E is nitrogen or methine; R38 is -CC13, phenyl or halogen-substituted phenyl; R39 and R40 independently of one another are hydrogen or halogen; and R41 is C1-C4alkyl; or a compound of the formula XII

in which R44 and R45 independently of one another are hydrogen or halogen
and
R46> R47 and R48 independently of one another are C1--C4alkyl.
14. A method for the selective control of weeds and grasses in crops of useful plants, wherein the useful plants, their seeds or seedlings or the area on which they are cultivated are treated with a herbicidally effective amount of a herbicide of the formula I and a herbicide-antagonistically effective amount of a safener of the formula X, XI or XII.
15. A composition according to claim 11, which contains spray tank adjuvants.
16. A composition according to claim 13, which contains spray tank adjuvants.


Documents:

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in-pct-2000-371-che-abstract.pdf

in-pct-2000-371-che-assignment.pdf

in-pct-2000-371-che-claims duplicate .pdf

in-pct-2000-371-che-claims original.pdf

in-pct-2000-371-che-correspondance others.pdf

in-pct-2000-371-che-correspondance po.pdf

in-pct-2000-371-che-description complete duplicate.pdf

in-pct-2000-371-che-description complete original.pdf

in-pct-2000-371-che-form 1.pdf

in-pct-2000-371-che-form 26.pdf

in-pct-2000-371-che-form 3.pdf

in-pct-2000-371-che-form 5.pdf

in-pct-2000-371-che-other documents.pdf

in-pct-2000-371-che-pct.pdf


Patent Number 206963
Indian Patent Application Number IN/PCT/2000/371/CHE
PG Journal Number 26/2007
Publication Date 29-Jun-2007
Grant Date 16-May-2007
Date of Filing 11-Sep-2000
Name of Patentee M/S. SYNGENTA PARTICIPATIONS AG
Applicant Address SCHWARZWALDALLEE 215, CH-4058 BASEL.
Inventors:
# Inventor's Name Inventor's Address
1 Jutta GLOCK, Rifeldweg 6, CH-4322 Mumpf
2 André STOLLER, 7, rue Charles Wolf, F-68730 Blotzheim
3 Michel MÜHLEBACH Bollwerkstrasse 30A, CH-4102 Binningen
4 Thomas MAETZKE, Wilhelm-Haas-Weg 12, CH-4142 Münchenstein
PCT International Classification Number C 07D498/04
PCT International Application Number PCT/EP1999/001593
PCT International Filing date 1999-03-11
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2431/98 1998-12-08 Switzerland
2 CH 1998 0616/98 1998-03-13 Switzerland