BG65411B1 - Method for reducing the phytotoxicity of herbicides - Google Patents

Abstract

The present invention provides a method of reducing phytotoxicity to crops (specially maize), caused by a herbicidal benzoylisoxasole and/or dione derivative of formula or an agriculturally acceptable salt or metal complex thereof. In the formula R2 has the meanings given in the description. The method comprises applying to the locus of the crop an antidotally effective amount of an antidote compound, optionally with a partner herbicide.

Description

Technical field

The present invention relates to protective herbicidal compounds, in particular to the protective derivatives of benzoylisoxazole and / or dione, which are used for growing crops, in particular maize (Zea mays), and to compositions used for such treatment.

BACKGROUND OF THE INVENTION

An important factor influencing the applicability of a herbicide is its selectivity to crops. In some cases, the useful crop is sensitive to the effects of the herbicide, which is applied in the required amount for application to control weed growth. In addition, some herbicidal compounds are phytotoxic to some weed species but not to others. This may make such herbicides unsuitable for controlling weeds in the presence of some crops. In order to be effective, the herbicide must cause minimal damage (preferably not harm) to the beneficial crop, while damage is maximum to the weed species that damage the crop site. Reducing herbicidal damage to crops without unacceptably reducing herbicidal action can be accomplished using crop protectors known as antidotes or safeners. Identifying an antidote that disrupts herbicide in crops is a complex task. The exact mechanism by which the antidote reduces herbicidal crop damage has not been established. In general, the neutralizing effect of the compound is specific to the herbicide and the culture where the active ingredients are administered. Benzoylisoxazoles are known to have herbicidal properties, for example EP 0418175, EP 0487357, EP 0527036 and EP 0560482. EP 0496630, EP 0496631, EP 0625505 and EP 0625508 describe some dione derivatives having herbicidal properties. Typically, such herbicides are very active against deciduous and grass weeds applied pre- and / or after emergence. The method of controlling growth with these compounds consists in administering a herbicidally active amount of the compounds, usually with an inert carrier or diluent over the area where a herbicidal control is desired. However, it has been found that herbicidal benzoylisoxazole and / or dione compounds in some cases have the opposite effect and impede the development of crops, in particular maize crops. The effectiveness of using these herbicides to control weeds in the presence of such crops may be enhanced by, or may in some cases require the addition of, a compound having an antidote to the herbicide.

Although it can be said in general terms that herbicides can be used in the presence of an antidote, it is a significant problem to identify a specific antidote for a specific crop with an appropriate degree of control of weed growth.

Applicants have found that certain compounds, in particular when administered as described below, are effective antidotes for crop protection, in particular maize from herbicidal damage or reduction of herbicidal damage caused by the administration of a certain amount of compound benzoylisoxazole and / or dione (optionally mixed with another herbicide), effective in controlling weed growth.

It is an object of the present invention to provide compositions of benzoylisoxazoles and / or dione herbicides in combination with an antidote, said compositions providing a reduction in crop damage, in particular maize (Zea Mays), due to the phytotoxicity of the herbicides and to the method for the administration of said herbicides and antidotes.

SUMMARY OF THE INVENTION

The present invention relates to a method of reducing phytotoxicity to a crop (in particular maize) in situ caused by the application of a herbicide derivative of benzoylisoxazole and / or a dione of formula (I):

65411 Bl

(^ ς) ζ in which A is a group from (A-l) to (A-7):

or respectively formula (A-ba) or (A-7a)

(A-7a)

wherein the position of the carbonyl group and group Q are reversed and the double bond in the ring is bonded to the carbon atom attached to the group Q; R is a hydrogen atom or a halogen atom; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing from one to six carbon atoms which is optionally substituted by one or more halogen atoms; a cycloalkyl group containing from 3 to 6 carbon atoms, optionally substituted by one or more groups R ⁵ , one or more halogen atoms or a group -CO ² R ³ ; or a group selected from -CO2R ^3, -COR ^5, cyano group, nitro group,

-CONR ³ R ⁴ and -S (O) _k R ¹³ ;

R ¹ is a straight or branched chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms, which is optionally substituted by one or more halogen atoms;

or a cycloalkyl group containing from three to six carbon atoms, optionally substituted by one to six groups R ⁵ or one or more halogen atoms;

R ² is a halogen atom; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; a straight or branched chain alkyl group containing up to six carbon atoms which is substituted by one or more groups -OR ⁵ ; or a group selected from a nitro group, a cyano group, -CO 2 R ⁵ , -S (O) p R ⁶ , -O (CH 2) mOR ⁵ , -COR ⁵ , -NR ⁿ R ' ² , -N (R ⁸ ) SO ² R ⁷ , -N (R ⁸ ) CO2R ⁷ , 20 -OR ⁵ , -OSO2R ⁷ , -SO2NR ³ R ⁴ , -CONR ³ R ⁴ -CSNR ³ R ⁴ , - (CR'R '°) yS (O) R ⁷ and -CF ₅ ;

or two R ² groups of adjacent phenyl ring carbon atoms, together with the carbon atoms to which they are attached, form a 25 to 7 membered saturated or unsaturated heterocyclic ring containing up to three ring heteroatoms selected from nitrogen, oxygen or sulfur, which ring is optionally substituted by one or more groups selected from halogen, nitro, 30 S (O) pR ¹³ , C 1-4 alkyl, C ₁₄ alkoxy, C ₁₄ haloalkyl, C _1-4 haloalkoxy, = 0 (or a 5- or 6-membered cyclic acetal thereof), and = NO-R ^3, it being understood that the sulfur atom present in the ring, may be in the form of d oup -SO- or -SO ₂ -;

z is an integer from one to five: when z is greater than one, the groups R ² may be the same or different;

R ³ , R ⁴ and R ^{09 are} each independently a hydrogen atom or a straight or branched chain alkyl group containing up to six carbon atoms which are optionally substituted by one or more halogen atoms;

R ⁵ and R ¹¹⁰ each independently are a straight or branched chain alkyl group 45 containing up to six carbon atoms which is optionally substituted by one or more halogen atoms or an alkenyl or alkynyl straight or branched chain group containing from two to six (preferably three to six) carbon50 native atoms which are optionally substituted by one

65411 B1 or more halogen atoms;

R ⁶ and R ⁷ , which may be the same or different, are each R ⁵ ; or phenyl, optionally substituted by one to five groups, which may be the same or different, selected from a halogen atom, a straight- or branched-chain alkyl group containing up to six carbon atoms which may be optionally substituted by one or more halogen atoms, nitro group, cyano group, -CO 2 R ⁵ , -S 1 O) p R ¹³ ; -NRNR ¹² , -OR ⁵ and -C'ONR'R ⁴ ;

R ⁸ , R ⁹ and R ¹⁰ are all carbon atoms or R ⁶ ;

R ¹² and R ¹² are each a carbon atom or R ⁵ ;

R ¹³ and R ¹ 'are each a straight or branched chain alkyl group containing up to six carbon atoms which are optionally substituted by one or more halogen atoms;

Q is a hydroxyl group, alkoxy, OR ¹¹² , SR ¹¹² or SR ¹ ;

L is oxygen or NR ^109;

R ¹⁴ , R ^14a , R ^14b , R ¹⁵ , R ^15a , R ^15b , R ¹⁶ , R ^16a , R ^16b , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are all the same or different groups selected from hydrogen, C 0, - (CH 2) uCO 2 R ¹⁰ , halogen, cyano, C 1-6 alkoxy, - (CH ₂ ) _x - [phenyl optionally substituted by one to five groups R ³ , which may be the same or different], and cycloalkyl containing from three to six carbon atoms optionally substituted by C _1-6 alkyl or -SiO ^ R ¹¹¹ ;

R ² is phenyl optionally substituted by one to five groups selected from halogen, C ₍₆ alkyl, C _1-3 haloalkyl, alkoxy and nitro group;

R ³ is a halogen selected group, R ¹¹⁴ , a nitro group, a cyano group, -CO 2 R ⁵ -S (O) p R ¹ , -OR ¹ h-NR ¹⁵ R ⁶ ;

R ⁴ is a straight or branched chain alkyl group containing one to three carbon atoms, optionally substituted by one or more halogen atoms;

rh5 _and R ^6, which may be identical or different, are each a hydrogen atom or R ^110;

p, q and and each independently are zero, one or two;

a whale each is one, two or three;

x is zero or one;

y is an integer of one to four; when y is greater than one, the groups R ⁹ and R ¹⁰ may be the same or different;

R ¹⁰ may be the same or different;

or an agriculturally acceptable salt or metal complex thereof; which method consists in administering the culture site, preferably before the herbicide compound, an effective amount of an antidote compound and an optional co-used herbicide.

Of course, said antidote is generally effective against said benzoylisoxazole or dione derivative.

It is understood, however, that antidotes used by the method of the present invention may form, for example, salts, and that the use of such salts is also within the scope of the present invention.

This patent description, including the accompanying claims, implies that the term "agro-culturally acceptable salts" means salts in which the cations or anions are known and accepted in the art of salt formation for use in agriculture or horticulture. Preferably, the salts are water soluble. Suitable base salts include alkali metal salts (eg sodium and potassium), alkaline earth metals (eg calcium and magnesium), ammonium radicals or amines (eg diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine). Suitable acid addition salts, for example formed from compounds of formula (I) containing an amino group, include salts of inorganic acids, for example hydrochlorides, sulfates, phosphates and nitrates, and salts of organic acids, for example acetic acid. It should be understood that the term "dione" as used in this specification, including the related claims, should not exclude the possible presence of additional C = O groups as in saws.

The term "metal complexes" means compounds in which one or both of the oxygen atoms of 1,3-dione of formula (A-3), (A-4), (A5), (A-6), (A-7) , (A-ba) or (A-7a) acts as a compound that forms a chelate to a metal cation. Examples of such metal cations are zinc, magnesium, cupr, cupr, ferri, ferro, titanium and aluminum cation.

The compounds of formula (I) may exist in enol tautomeric forms which

65411 B1 can lead to an increase in geometric isomers around the enol double bond. In addition, in some cases the above substituents may contribute to the formation of optical isomers and / or stereoisomers. All these forms and mixtures thereof are within the scope of the present invention.

It is to be understood that in the present specification the compounds containing a cyclohexane ring corresponding to formula (A-6) or (A-7) or their starting compounds include the compounds of the corresponding formula (A6a) or (A-7a) or starting materials their compounds.

The definitions of the designations in the description, including the claims, unless otherwise indicated, generally apply the definitions below to the radicals of formula (I), (la), (lb):

"Halogen" means a fluorine, chlorine, bromine or iodine atom; and the alkyl groups and moieties have a straight or branched chain and contain from 1 to 6 carbon atoms.

Preferably, A is a group of formula (A1), (A-2), (A-3) or (A-4) (the compounds of formula (A-1) are most preferred).

The benzoyl ring of the compounds of formula (I) is preferably 2,4-disubstituted,

2,3-double or 2,3,4-tri-substituted.

Preferably in formulas (A-4) to (A7) the groups R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² , R ^14a , R ^15a , R ^16a , R ¹⁰³ , R ^14b , R ^15b , R ^16b , R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ ca are all hydrogen or lower alkyl (preferably hydrogen, methyl or ethyl); L (in A-7a) is NH; and Q is a hydroxyl group or -S-phenyl.

Compounds of formula (I) wherein A is (A1), (A-2) or (A-3); R is hydrogen or -CO ₂ R ³ (in A-1 or A-2), where R ³ is a straight or branched-chain alkyl group containing up to three carbon atoms; and R ¹ is cyclopropyl are preferred.

Another preferred class of compounds of formula (I) in which A is (A-1) are those in which:

R is hydrogen or -CO ₂ Et;

R ¹ is cyclopropyl;

and two groups R ² of adjacent carbon atoms of the phenyl ring, together with the carbon atoms to which they are attached, may combine to form a 5- or 6-membered saturated or unsaturated heterocyclic ring fused to 2.3 or 3,4 positions of the benzoyl ring; wherein the heterocyclic ring contains two heteroatoms selected from sulfur or oxygen that are attached to the 2 and 3 or 3 and 4 positions of the benzoyl ring; and wherein the 4 benzoyl ring substituent is halogen or S (O) _p Me, or the 2 benzoyl ring substituent is methyl, S (O) _p Me or CH ₂ S (O) _q Me, respectively; and optionally the heterocyclic ring may be substituted by one or more halogen atoms.

Another preferred class of compounds of formula (I) are those wherein A is (A-1); R is hydrogen or -CO ₂ Et; R ¹ is cyclopropyl; R ² is a halogen atom or a group selected from -CF ₃ , Me, Et, S (O) _p Me, -CH ₂ S (O) _q Me and optionally halogenated methoxy or ethoxy and z is two or three.

Another preferred class of compounds of formula (I) in which A is (A-4) are those in which:

R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² are all hydrogen;

and two groups R ² of adjacent carbon atoms of the phenyl ring, together with the carbon atoms to which they are attached, may combine to form a 6-membered saturated heterocycle which is fused to 2,3 or

3,4 positions of the benzoyl ring; wherein the heterocyclic ring contains a sulfur atom which is attached at the 4-position of the benzoyl ring preferably in the form of a group -SO or -SO ₂ - and which ring is substituted by 5- or

6-membered its acetal.

A more preferred class of compounds of formula (I) is of formula (1a):

are the ones where

R is hydrogen or -CO ₂ Et;

R ⁷ is selected from -S (O) _p Me, Me, Et, chlorine, bromine and fluorine atom, methoxy group, ethoxy group and -CH ₂ S (O) _q Me;

R ¹¹⁸ is selected from hydrogen atom, chlorine, bromine and fluorine atom, methoxy group, ethoxy

65411 B1 group and -S (O) _p Me;

R ¹¹⁹ is selected from hydrogen atom, chlorine, bromine and fluorine atom, methoxy group and CF ₃ ; and p and q each independently have values of zero, one or two.

Particularly preferred is a class of compounds of formula (I) having the formula (Ib):

wherein R ¹²⁰ is chlorine, bromine or trifluoromethyl; and

R is hydrogen or -CO ₂ Et.

Preferred dions are those in which the substituted phenyl ring, as defined in formula (I), (1a) or (Ib) is attached to the group:

Such dions in which the phenyl ring is substituted by two groups, each independently selected from halogen, alkyl 8 (O) _p alkyl (p = 0, 1 or 2) and haloalkyl are also preferred.

Preferred saws are those in which the substituted phenyl ring, as defined above, is attached to the group:

The following compounds of formula (I) are among the most preferred for use according to the present invention:

5-cyclopropyl-4- [2-chloro-3-ethoxy-4 (ethylsulfonyl) benzoyl] isoxazole;

4- (4-chloro-2-methylsulfonylbenzoyl) -5cyclopropylisoxazole;

5- cyclopropyl-4- (2-methylsulfonyl-4trifluoromethylbenzoyl) isoxazole;

4- (4-bromo-2-methylsulfonylbenzoyl) -5cyclopropylisoxazole;

5-cyclopropyl-4- [4-fluoro-3-methoxy-2 (methylsulfonyl) benzoyl] isoxazole;

4- (4-bromo-2-methylsulfonylmethyl6enzoyl) -5-cyclopropylisoxazole;

ethyl 5-cyclopropyl-4- (2-methylsulfonyl4-trifluoromethylbenzoyl) isoxazole-3-carboxylate;

2- [2-chloro- (4-methylsulfonyl) benzoyl] -

1,3-cyclohexanedione;

2- [2-Nitro- (4-methylsulfonyl) benzoyl] -

1,3-cyclohexanedione;

2- (2,3-dihydro-5,8-dimethyl-1,1-dioxospiro [4H-1-benzothiine-4,2 '- [1,3] dioxolane] -6ylcarbonyl) cyclohexane-1,3-dione;

5- cyclopropyl-4- (2-methylsulfonyl-4trifluoromethylbenzoyl) -3-methylthioisoxazole; and

2-cyano-3-cyclopropyl-1- (2-methylsulfonyl-4-trifluoromethylphenyl) propane-1,3-dione.

Most preferred compounds are 5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzoyl) isoxazole and 2- [2-nitro- (4-methylsulfonyl) benzoyl] -1,3-cyclohexanedione.

The herbicidal benzoylisoxazole and / or dione compounds for use according to the present invention may be prepared by the methods described in the aforementioned patent publications or by the application or adaptation of known methods used or described in the chemical literature.

It has been found that the antidote compounds mentioned above can be selected from a variety of chemical substances. Preferred compounds of the present invention may include one or more antidotes not implicit in the previous antidotes that are proposed for use with benzoylisoxazole and / or dione derivatives of formula (I). The compounds of the present invention may include one or more of the following antidotes:

a) compounds of formula (II) and (III),

65411 Bl

wherein:

15 _m / RIO (III) n 'is an integer from 0 to 5, preferably from 0 to 3;

T is a (C or C ₂ ) -alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C) -alkyl radicals or by [(C 1 -C 4 -alkoxy) carbonyloxy;

W is an unsubstituted or substituted divalent heterocyclic radical selected from the group of partially unsaturated or aromatic five membered heterocyclic rings having 1 to 3 N or O atoms in the heterocycle, wherein the ring contains at least one nitrogen atom and no more than one O atom , preferably a radical selected from the group consisting of (WJ to (W ₄ ),

COOR2 »

(W1) (W2) m 'is 0 or 1;

R ¹⁷ and R ¹⁹ are the same or different halogen, (C 1 -C 4 alkyl, (C ₁ -C ₄ ) alkoxy, nitro group or (C ₁ -C ₄ ) haloalkyl;

R 18 _and J 20 _{are the same or} different OR ²⁴ , SR ²⁴ or NR ²⁴ R ²⁵ or a saturated or unsaturated 3 to 7 membered heterocyclic compound having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group selected from O and S which is attached to the carbonyl group in (II) or (III) by a nitrogen atom and is unsubstituted or substituted by radicals selected from the group consisting of (C (-C 4) alkyl, (C 1 -C 4) alkoxy or optionally substituted phenyl, preferably a radical of formula OR ²⁴ , NHR ²⁵ or N (CH 3) ₂ , especially formula OR ²⁴ ;

R ²⁴ is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of from 1 to 18 C atoms,

R ²⁵ is hydrogen, (C 1 -C 4 alkyl), (C 1 -C 4 alkoxy, or substituted or unsubstituted phenyl;

R ²⁶ is hydrogen, (C ₁ -C ₈₎ alkyl, (C _| -C ₈₎ haloalkyl, (C, -C ₄₎ alkoxy- (C -C ₄₎ -alkyl, (C] _-C6) hydroxyalkyl , (C ₃ -C ₁₂ ) cycloalkyl or three

- (C ₍ -C ₄ ) -alkyl-silyl; and

R ²⁷ , R ²⁸ , R ²⁹ are the same or different hydrogen, (C 1 -C ₈ ) alkyl, (C 1 -C ₈ ) haloalkyl, (C ₃ C ₂ ) cycloalkyl or substituted or unsubstituted 5 phenyl;

B) one or more compounds selected op

4.6-dichloro-2-phenylpyrimidine (fenclorim), benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole),

B1- (4-methylphenyl) -N- (1-methyl-1-phenylethyl) urea (dymuron),

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea;

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylcarbamide;

1- [4- (L4-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methyl urea;

1- [4- (1,1-naphthoylsulfamoyl) phenyl] -3,3 dimethylurea; or (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, (P, B) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),

4- (2,4-dichlorophenoxy) butyric acid (2,4-DB),

4-chloro-o-tolyloxy) acetic acid (MCPA),

4- (4-chloro-o-tolyloxy) butyric acid,

4- (4-chlorophenoxy) butyric acid,

3.6-dichloro-2-methoxybenzoic acid 35 (dicamba),

- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloro), and salts and esters thereof, preferably (C 1 -C ₈ ); or (±) -4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benzoxacor),

N, N-diallyl-2,2-dichloroacetamide (dichloromide), (B, S) -3-dichloroacetyl-5- (2-furyl) -2,245 dimethyloxazolidine (furylazole),

N- (4-chlorophenyl) maleimide (CMPI),

4-hydroxy-1-methyl-3- (1 -1H-tetrazol-5ylmethanoyl) -1H-quinolin-2-one, (S) -1- (1-alpha-methylbenzyl) -3-p-tolyl car50 bamide ((S) -MBU) and

65411 Bl

S-1-methyl-phenylethyl piperidine-1-carbothioate (dimepiperate).

c) N-acylsulfonamides of formula (IV) or salts thereof;

( ^R32 ) n (IV) in which

R ³⁰ is hydrogen, or R ³⁰ is a hydrocarbon radical, hydrocarbon oxy radical, hydrocarbon radical or heterocyclyl radical, which is preferably bonded through a carbon atom, which radicals are unsubstituted or substituted by one or more halogen selected groups, a cyano group, a nitro, an amino group, a hydroxyl group, a carboxyl, a formyl, a carboxamide, a sulfonamide and radicals of formula Z ^a- R ^a , each hydrocarbon residue preferably having 1 to 20 carbon atoms and a carbon-containing radical R ³⁰ include substituents which for preferred having 1 to 30 carbon atoms;

R ³¹ is hydrogen or (C 1 -C 4 -alkyl, preferably hydrogen, or

R ³⁰ and R ³¹ together with the group of formula -CON- are the residue of a 3- to 8-membered saturated or unsaturated ring;

R ³² is identical or different halogen, cyano group, nitro group, amino group, hydroxyl, carboxyl, formyl, CONH ₂ , SO ₂ NH ₂ or a radical of formula Z ^b -R ^b ;

R ³³ is hydrogen or (C 1 -C ₄ ) -alkyl, preferably hydrogen,

R ³⁴ is the same or different halogen, cyano group, nitro group, amino group, hydroxyl, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ or a radical of formula Z ^c- R ^c ;

R ^a is a hydrocarbon radical or heterocyclic radical, which radicals are unsubstituted or substituted by one or more groups, which may be the same or different, selected from the group halogen, cyano, nitro, amino, hydroxyl, mono- and di [(C 1 -C ₄ ) -alkyl] amino, or an alkyl radical, in which most, preferably 2 or 3, non-adjacent CH ₂ groups are in each case displaced by one oxygen atom;

R ^b and R ^c are the same or different hydrocarbon radical or heterocyclic radical, which radicals are unsubstituted or substituted by one or more groups, which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halo- (C 1 -C ₄ ) -alkoxy, mono- and di [(C ₍ -C ₄ ) -alkyl] amino, or alkyl radical in which several, preferably 2 or 3, non-adjacent CH ₂ groups are in each case substituted by one oxygen atom;

Z ^a is a divalent group of formula O, S, CO, SC, CO-O, CO-S, O-CO, S-CO, SO, SO 2, NR *, CO-NR *, NR * -CO, SO 2 - NR * or NR * -SO2, the bond on the right side of each of the divalent groups being the bond to the radical R ^a and the radicals R * each independently of one another are hydrogen, (C 1 -C 4) -alkyl or halo- (C ₁ -C ₄ ) apkyl;

Z ^b and Z ^{c are} each independently a direct bond or a divalent group of formula O, S, CO, CS, CO-O, CO-S, O-CO, S-CO, SO, SO2, NR *, SO2 -NR *, NR * -SO2, CO-NR * or NR * -CO, where in the asymmetric divalent groups the atom on the right side is attached to the radical R ^b or R ^c and where the radicals R * are each independently hydrogen; (C 1 -C 4) -alkyl or halo-C 1 -C 4 -alkyl;

η is an integer from 0 to 4, preferably 0, 1 or 2, in particular 0 or 1, and t is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2;

d) acylsulfamoylbenzamides of formula (V) or salts thereof:

wherein

X ³ is CH or N,

R ³⁵ is hydrogen or a heterocyclic or hydrocarbon radical, which radicals are optionally substituted by one or more groups, which may be the same or different, selected from

65411 B1 of halogen, cyano group, nor group, amino group, hydroxyl, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ and Z ^d -R ^d ;

R ³⁶ is hydrogen, a hydroxyl group; or R ³⁶ is (C 1 -C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) alkynyl, (C _t -C ₆ ) -anKOKCH, (C ₂ -C ₆ ) -alkenyloxy, which radicals are optionally substituted by one or more groups, which may be the same or different, selected from halogen, hydroxyl group, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy and (C 1 -C ₄ ) alkylthio, or

R ³⁵ and R ³⁶ together with the nitrogen atom to which they are attached are a 3- to 8-membered saturated or unsaturated ring;

R ³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^e -R ^e ;

R ³⁸ is hydrogen, (C ₁ -C ₄ ) -alkyl, (C ₂ -C ₄ ) -alkenyl or (C ₂ -C ₄ ) -alkynyl;

R ³⁹ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl CHO, CONH ₂ , SO ₂ NH ₂ or Z ^f -R ^f ;

R ^d is a (C 2 -C 20) -alkyl radical, the hydrocarbon chain of which is interrupted by one or more oxygen atoms; or R ^d is a heterocyclic or hydrocarbon radical, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, cyano group, nitro group, amino group, hydroxyl group, mono- and di- [(C 1 -C ₄ ) -alkyl] amino;

R 1 and R ^f are the same or different (C 2 -C 20) alkyl radical of the hydrocarbon chain which is interrupted by one or more oxygen atoms; R 1 and R ^f are the same or different heterocyclic or hydrocarbon radicals, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl, phosphoryl, (C 1 -C 4) -haloalkoxy, mono- and di [(C 1 -C ₄ ) -alkyl] amino;

Z ^d is a divalent unit selected from the group consisting of O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *, C (O) NR * or SO ₂ , NR *;

Z ^c and Z ^f are the same or different and are a direct bond or a divalent unit selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *, SO ₂ NR * and C (O) NR *;

R * is hydrogen, (C 1 -C ₄ ) -alkyl or (C ₍ -C ₄ ))

-haloalkyl;

s is an integer from 0 to 4, and o is an integer from 0 to 5 when X is CH, or is an integer from 0 to 4 when X is N;

f) a compound of formula (VI):

(VI) in which:

R ⁴⁰ is hydrogen, (C 1 -C 4) -alkyl, (C 1 -C 4) alkyl substituted by (C 1 -C 4) -alkyl-X ⁴ or (C 1 -C 4) haloalkyl-X ⁴ , (C] -C4) -haloalkyl, NO2, CN, -COO-R ⁴³ , NR / ⁴ , SO, NR, ⁴⁵ or CONR2 ⁴⁶ ;

R ⁴¹ is hydrogen, halogen, (C 1 -C ₄ ) -alkyl, CF ₃ , (C 1 -C ₄ ) -alkoxy or (C 1 -C 4 -haloalkoxy;

R ⁴² is hydrogen, halogen or (C 1 -C ₄ ) -alkyl;

Q ¹ , Q ² , E and G are the same or different O, S, CR ⁴⁷ , CO, NR ⁴⁸ or a group of formula (VII):

in case that:

i) at least one of the groups Q ¹ , Q ² , E and G is a carbonyl group, that exactly one of these groups is a radical of formula (VII) and that the group of formula (VII) is close to the carbonyl group, and ii) two adjacent groups Q ¹ , Q ² , E and G cannot be simultaneously oxygen;

R ⁴ is the same or different hydrogen or (C 1 -C 8) -alkyl, or both radicals R ⁴ together are (C 2 -C ₆ ) -alkylene;

V is Y ³ -R ^h or NR ₂ ⁴⁹ ;

X ⁴ is O or S (O);

Y ³ is O or S;

R ^h is hydrogen, (C] -C ₈₎ -alkyl, (C] -C ₈₎ haloalkyl, _{(C] -C4)} -alkoxy- (C _| -C ₈₎ -alkyl, (C ₃ -C ₆ ) -alkeniloksi- (C _| -C ₈₎ -alkyl, or phenyl- (C] -C ₈₎ -alkyl, where the phenyl ring is optionally substituted by hydrogen, (C] -C ₄₎ -alkyl, CF _3, methoxy

65411 B1 or methyl-8 (O) _x ; (C ₃ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -haloalkenyl, phenyl- (C ₃ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) -alkynyl, phenyl- (C ₃ -C ₆ -alkynyl, oxetanyl, furfuryl or tetrahydrofuryl;

R ⁴³ is hydrogen or (C 1 -C ₄ ) -alkyl;

R ⁴⁴ is hydrogen, (C 1 -C 5 -alkyl, (C 1 -C 4) -alkylcarbonyl or the two radicals R ⁴⁴ together are (C 4 -C ₅ ) -alkylene;

R ⁴⁵ and R ⁴⁶ are the same or different hydrogen, (C 1 -C 4) -alkyl or the two radicals R ⁴⁵ and / or R ⁴⁶ together are (C 4 -C ₅ ) -alkylene, where one CH ₂ group may be substituted by O or S or one or both groups of CH ₂ may be substituted by NR ';

R ¹ is hydrogen or (C 1 -C ₈ ) -alkyl;

R ⁴⁷ is hydrogen, (C ₁ -C ₆ -alkyl, or both radicals R ⁴⁷ together are (C ₂ -C ₆ ) -alkylene;

R ⁴⁸ is hydrogen, (C 1 -C ₈ ) -alkyl, substituted or unsubstituted phenyl or benzyl, which is unsubstituted or substituted on the phenyl ring.

R ⁴⁹ is hydrogen, (C 1 -C 4 -alkyl, phenyl, phenyl-C 1 -C 6 -alkyl, the phenyl rings of which may also be substituted by F, Cl, Br, NO 2> CN, OCH 3, (C] - C4-alkyl or CH3SO2; (C1-CJ-alkoxy- (C [-C8] -alkyl, (C3-C6) -alkenyl, (C3-C6) alkynyl, (C3-C6) -cycloalkyl, or two radicals R ⁴⁹ are both (C 4 -C ₅₎ -alkylene, where the group CH ₂ may be replaced by O or S or one or two groups CH ₂ may be replaced by NR ^k;

R ^k is hydrogen or (C 1 -C ₄ ) -alkyl;

m 'is 0 or 1 and is 0, 1 or 2;

including stereoisomers and agro-culturally acceptable salts.

Unless otherwise defined, the following definitions of the radicals of formula (II) to (VII) are generally applicable.

The alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, and alkylthio radicals and the corresponding unsaturated and / or saturated radicals may in each case be straight or branched chain in the carbon structure. Alkyl radicals, also constituents such as alkoxy, haloalkyl and the like, preferably have 1 to 4 carbon atoms and are for example methyl, ethyl n- or i-propyl or η-, i-, t- or

2-butyl. Alkenyl and alkynyl radicals mean unsaturated radicals, which may correspond to alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl,

2-methylprop-2-en-1-yl, 6ut-2-en-1-yl, but-3-en-

1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en1-yl. Alkynyl is for example propargyl, but-2-yn-

1-yl, but-3-yn-1-yl, L-methylbut-3-yn-yl / XC] C _1-4 alkyl "is for example an abbreviation for alkyl having 1 to 4 carbon atoms; the same applies analogously to other general definitions of radicals in which the order of the possible numbers of carbon atoms is given in parentheses.

Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7 and especially preferably 3 to 6 carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl are respectively unsaturated compounds.

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl which are partially or fully substituted by halogen, preferably fluorine, chlorine and / or bromine, in particular fluorine or chlorine, for example CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHC1, CC1 ₃ , CHC1 ₂ , CH ₂ CH ₂ C1.

Haloalkoxy is, for example, OCF ₃ , OCHF ₂ , OCH ₂ F, CF ₃ CF ₂ O, OCH ₂ CF ₃ and OCH ₂ CH ₂ C1. This applies similarly to other halogen substituted radicals. The hydrocarbon radical may be an aromatic or aliphatic hydrocarbon radical, wherein the aliphatic hydrocarbon radical is usually a straight or branched chain, saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, especially preferably 1 to 12, carbon atoms, e.g. alkenyl or alkynyl. An aliphatic hydrocarbon radical preferably means alkyl, alkenyl or alkynyl having up to 12 carbon atoms; the same applies analogously to an aliphatic hydrocarbon radical in a hydrocarbon radical.

Aryl is typically a mono-, bi-, or polycyclic aromatic system which preferably has 6-20 carbon atoms, preferably 6 to 14 carbon atoms, especially preferably 6 to 10 carbon atoms, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl , pentalenyl and fluorenyl, especially preferably phenyl.

A heterocyclic ring, heterocyclic radical or heterocyclyl is mono-, bi- or poly

65411 B1 cyclic ring system which is saturated, unsaturated and / or aromatic and contains 1 or more, preferably 1 to 4 heteroatoms, preferably selected from the group consisting of N, S and O.

Saturated heterocyclic rings having 3 to 7 ring atoms and one or two heteroatoms selected from the group consisting of Ν, O and S are preferred, their halogens not adjacent. Particularly preferred are monocyclic rings of 3 to 7 atoms and a heteroatom selected from the group consisting of Ν, O and S and also morpholine, dioxalan, piperazine, imidazoline and oxazolidine. Very particularly preferred heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.

Partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms selected from the group consisting of Ν, O and S. Also preferred are partially unsaturated heterocycles with 56 atoms in the ring and one heteroatom selected from the group consisting of of Ν, O, and S. Particularly particularly preferred partially unsaturated heterocycles are pyrazoline, imidazoline, and isoxazoline.

Equally preferred is heteroaryl, for example mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms containing one to four heteroatoms selected from the group consisting of Ν, O and S, the halogens not being adjacent. Particularly preferred are monocyclic aromatic heterocycles having a 5-6-atom ring which includes a heteroatom selected from the group consisting of Ν, O and S and also pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole and pyrazole isoxazole. Pyrazole, thiazole, triazole and furan are particularly preferred.

Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl such as phenyl and arylalkyl and as benzyl or substituted heterocycle, are a substituted radical derived from an unsubstituted carbon skeleton, the substituents being preferably one or more, preferably 1 or more, preferably , 2 or 3, in the case of C1 and F to the maximum possible number of substituents selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, and alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, and in the case of cyclic alkyl saturated hydrocarbon-containing substituents, preferably alkenyl, alkynyl, alkenyloxy and alkinyloxy. In the case of radicals having carbon atoms, preferably those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. As a rule, preferred substituents are those selected from the group consisting of halogen, for example fluorine or chlorine, (C _| -C ₄₎ -alkyl, preferably methyl or ethyl, (C ₁ -C ₄₎ -haloalkyl, preferably trifluoromethyl, (C SD-alkoxy, preferably methoxy or ethoxy, (C _| -C ₄₎ -haloalkoxy, nitro and cyano. particularly preferred in this context are the substituents methyl, methoxy and chlorine.

A mono- or disubstituted amino group is a chemically stable radical selected from the group consisting of substituted amino radicals that are N-substituted for example one or two identical or different radicals selected from the group consisting of alkyl, alkoxy, acyl and aryl, for preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkylN-arylamino or N-heterocycles. In this context, alkyl radicals having 1 to 4 carbon atoms are preferred. Preferably, the aryl is phenyl. Preferably the substituted aryl is phenyl. The definition below refers to acyl, preferably (C 1 -C 6 alkanoyl. This also applies analogously to substituted hydroxylamino or hydrazino.

Preferably, the optionally substituted phenyl is phenyl which is unsubstituted or mono- or polysubstituted, preferably to trisubstituted, in the case of a halogen such as Cl and F also to five-substituted with identical or different radicals selected from the group consisting of halogen, ( A C ₁ -C ₄ alkyl, (C 1 -C ₄ ) -alkoxy, (C 1 -C ₄ ) -haloalkyl (C 1 -C ₄ ) -haloalkoxy and nitro group, such as a ο-, β- and β- tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl,

2,4-, 3,5-, 2,5-and 2,3-dichlorophenyl, ο-, m- and p

65411 B1 methoxyphenyl.

An acyl radical is an organic acid radical which preferably has up to 6 carbon atoms, for example, a carboxylic acid radical and radicals of derivatives thereof, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acid or a carbonyl monoester radical N-substituted, optionally carbamic acids, sulfonic acid, sulfinic acids, phosphonic acids, phosphinic acids. The acyl is, for example, formyl, alkylcarbonyl, such as (C ₁ -C ₄ -alkyl) carbonyl, phenylcarbonyl, optionally substituted by the phenyl ring, for example as indicated above for phenyl or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl or alkylsulfonyl B1-alkyl-1-iminoalkyl.

Formulas (II) to (VII) are considered to include all stereoisomers and mixtures thereof. Stereoisomers include enantiomers, diastereomers and Z and E isomers.

Preferred herbicide / antidote combinations are those containing an antidote of formula (II) and / or (III), where the designations and indices have the following meanings:

R ²⁴ is hydrogen, (C 1 -C ₁₈ ) -alkyl, (C ₃ -C ₁₂ ) -cycloalkyl, (C ₂ -C ₁₈ ) -alkenyl and (C ₂ -C ₁₈ ) alkynyl, in which the carbon-containing groups may be substituted by one or more, preferably up to three, R ⁵⁰ radicals;

R ⁵⁰ is the same halogen, hydroxyl group, (C 1 -C ₈ ) -alkoxy, (C 1 -C 8 -alkylthio, (C ₂ -C ₈ ) -alkenylthio, (C ₂ -C ₈ ) -alkynylthio, (C ₂ -C ₈ ) alkenyloxy, (C ₂ -C ₈ ) -alkynyloxy, (C ₃ -C ₇ ) cycloalkyl, (C ₃ -C ₇ ) -cycloalkoxy, cyano group, mono- and di- (C) - C ₄ ) -alkylamino, carboxyl, (C) -C ₈ ) -alkoxycarbonyl (C ₂ -C ₈ ) -alkenyloxycarbonyl, (C ₂ -C ₈ ) -alkenylthiocarbonyl, (C ₂ -C ₈ ) alkynyloxycarbonyl, (C ₍ -C ₈ -alkylcarbonyl, (C ₂ -C ₈ ) -alkenylcarbonyl, (C ₂ -C ₈ ) -alkynyl carbonyl, 1- (hydroxyamino) - (C ₁ -C ₈ ) -alkyl, 1 - [(C ₂ -C ₄ -alkylimino] - (C ₁ -C ₄ ) -alkyl, 1 - [(C ₂ -C ₈ ) -alkoxyimino] - (C ₁ -C ₆ ) -alkyl, (C 1 -C ₈ ) - a alkylcarbonylamino, (C ₂ -C ₈ ) -alkenylcarbonylamino, (C ₂ -C ₈ ) alkynylcarbonylamino, aminocarbonyl, (C 1 -Cylinders lamecarbonyl, di- (C 1 -C ₆ ) -alkylaminocarbonyl, (C ₂ -C ₆ ) -alkenylaminocarbonyl, (C ₂ -C ₆ ) alkynylaminocarbonyl, (C ₁ -C ₈ ) -alkoxycarbonylamino, (C 1 -C ₈ ) -alkylaminocarbonylamino, (C 1 -C ₆ ) -alkylcarbonyloxy, which is unsubstituted or substituted by R ⁵¹ or is (C 2 -C 6) -alkenylcarbonyloxy, (C 2 -C 6) -alkynylcarbonyloxy, (C 1 -C 6) -alkylsulfonyl, phenyl, phenyl- (C 1 -C 6) -alkoxy, phenyl- (C 1 -C 6) -alkoxycarbonyl, phenoxy, phenoxy- (C 1 -C 6) -alkoxy, phenoxy- (C 1 -C 6) -alkoxycarbonyl, f nilkarboniloksi, phenylcarbonylamino, phenyl- (C, -C6) -alkylcarbonylamino, it is said last 9 radicals to be unsubstituted or mono- or polysubstituted, preferably up to trisubstituted by radicals R ^52, SiR'3, OSiR _'3, R' ₃ Si '- (C ₁ -C _g ) -anKOKCH, CO-O-NR' ₂ , ON = CR '_2> N = CR' ₂ , O-NR ' ₂ , NR' ₂ , CH (OR ') ₂ , O- (CH ₂ ) _q -CH (OR ') ₂ , CR "' (OR ') ₂ , O- (CH ₂ ) _w CR"' (OR ") _2j or by R" O-CHR "'CHCOR" - (C 1 -C ₆ ) -alkoxy,

R ⁵¹ is the same or different halogen, nitro group, (C ₁ -C ₄ ) -alkoxy and phenyl which is unsubstituted or substituted by one or more, preferably up to three, R ⁵² radicals;

R ⁵² is the same or different halogen, (C ₁ -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, (C 1 -C ₄ ) -haloalkyl, (C) -C ₄ ) -haloalkoxy, or nitro group;

R 'is the same or different hydrogen, (C 1 -CJ-alkyl, phenyl which is unsubstituted or substituted by one or more, preferably up to three, R ⁵² radicals, or two radicals R' together form (C ₂ -C ₆ a) -alkanediyl chain;

R 'is the same or different (C 1 -C ₄ ) alkyl, or two radicals R' together form a (C ₂ -C ₆ ) -alkanediyl chain;

R 'is hydrogen or (C 1 -C ₄ ) -alkyl; and w is 0, 1, 2, 3, 4, 5 or 6.

Particularly preferred are herbicide / antidote combinations according to the invention that contain an antidote of formula (II) and / or (III), in which the designations and indices have the following meanings:

R ²⁴ is hydrogen, (C 1 -C ₈ ) -alkyl or (C ₃ -C ₇ ) cycloalkyl, said carbon radicals being unsubstituted or mono- or polysubstituted by halogen or mono- or disubstituted, preferably monosubstituted by the R ⁵⁰ radicals,

R ⁵⁰ is the same or different from the hydroxyl group (C 1 -C ₄ ) -alkoxy, carboxyl group, (C ₁ -C ₄ ) -alkoxycarbonyl, (C ₂ -C ₄ ) -alkenyloxycarbonyl, (C ₂ -C ₄ ) - alkynyloxycarbonyl, 1 (hydroxyimino) - (C ₁ -C ₄ ) -alkyl, 1 - [(C] -C ₄ ) -al

65411 B1 carbamino-N-C 1 -C 6 -alkyl and N - [(C 1 -C 4 -alkoxyimino-N-C 1 -C 6 -alkyl; SiR ' ₃ , ON = CR' ₂ , N = CR ' ₂ , NR' ₂ and ONR ' ₃ , wherein R 'is identical to or different from hydrogen, (C ₁ -C ₄ ) -alkyl, or as a pair of (C ₄ -C ₅ ) -alkanediyl chain, R ²⁷ , R ²⁸ and R ²⁹ are the same or different from hydrogen, (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₆ ) -haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl which is unsubstituted or substituted by one or more groups selected from halogen, cyano, nitro a group, an amino group, mono- and di - [(C 1 -C ₄ ) alkyl] amino, (C 1 -C ₄ ) -alkyl, (C 1 -C 4 -haloalkyl, (C 1 -C ₄ ) -alkoxy, (Cj-CJ-haloalkoxy, _(C} C _A) alkylthio and (C ₁ -C ₄₎ -alkylsulfonyl;

R ²⁶ is hydrogen, (C 1 -C 6 -alkyl, (C ₁ -C ₈ ) haloalkyl, (C 1 -C ₆ -alkoxy) -C ₁ -C ₆ -alkyl, (C ₁ -C ₆ ) -alkyl, (C ₁ - C ₆ -hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl or tri- (C ₁ -C ₄ ) -alkylsilyl,

R ¹⁷ and R ¹⁹ are the same or different halogen, methyl, ethyl, methoxy, ethoxy (C ₁ or C ₂ ) haloalkyl, preferably hydrogen, halogen or (C or C ₂ ) haloalkyl.

Antidotes in which the designations and indices in formula (II) have the following meanings are particularly preferred:

R ¹⁷ is halogen, nitro or (C 1 -C ₄ ) haloalkyl;

η is 0, 1, 2 or 3;

R ¹⁸ is a radical of formula OR ²⁴ ,

R ²⁴ is hydrogen, (C 1 -C ₈ ) -alkyl or (C ₃ -C ₇ ) cycloalkyl in which the aforementioned carbon-containing radicals are unsubstituted or mono- or polysubstituted, preferably trisubstituted, of the same or different halogen radicals, or up to disubstituted, preferably monosubstituted, by identical or different radicals selected from the group consisting of hydroxyl, (C ^ CJ-alkoxy, (C, -C ₄₎ alkoxycarbonyl, (C ₂ -C ₆₎ -alkeniloksikarbonil , (C ₂ -C ₆ ) -alkynyloxycarbonyl, 1- (hydroxyimino) - (C ₁ -C ₄ ) -alkyl, 1 - [(C ₃ C ₄ ) -alkylimino] (C 1 -C ₄ ) -alkyl, 1 - [(C, -C ₄₎ -alk coke ino] - (C, -C ₄₎ alkyl and radicals of the formula SiR _'3, ON = CR' _2, N = CR _'2, NR' ₂ and O-NR _'3, in which the radicals R' in the above formula are identical or different hydrogen, (C ₁ -C ₄ ) -alkyl or as a pair are (C ₄ or C ₅ ) -alkanediyl;

R ^27, R ²⁸ and R ²⁹ are identical or different hydrogen, (C, -C ₈₎ -alkyl, (C _| -C ₆₎ -haloalkyl, _{(C3 -C7)} -cycloalkyl or phenyl, which is unsubstituted or substituted from one or more radicals selected from halogen, (C 1 -C 6 -alkyl, (C 1 -C 4 -alkoxy, nitro group, (C 1 -C ₄ ) -haloalkyl and (C 1 -C ₄ ) haloalkoxy, and

R ²⁶ is hydrogen, (C ₁ -C ₈ ) -alkyl, (C 1 -C ₈ ) haloalkyl, (C 1 -C ₆ -alkoxy) C 1 -C ₆ -alkyl, (C 1 -C ₆ ) -hydroxyalkyl, (C ₃ -C ₇₎ -cycloalkyl or tri- (C _t -C ₄₎ -alkylsilyl.

Particularly preferred are also antidotes of formula (III), in which the designations and indices have the following meanings:

R ¹⁹ is halogen or (C 1 -C 4 -haloalkyl;

n 'is 0, 1, 2 or 3, where (R ¹⁹ ) _n is preferably 5-Cl

R ²⁰ is a radical of formula OR ²⁴ ,

T is CH ₂ or CH (COO- (C 1 -C ₃ ) -alkyl) and

R ²⁴ is hydrogen, (C ₁ -C ₈ ) -alkyl, (C ₁ -C ₈ ) -haloalkyl or (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, preferably (C] -C ₈ ) -alkyl.

Particularly preferred are an antidote of formula (II), in which the designations and indices have the following meanings:

We (W1);

R ¹⁷ is halogen or (C 1 -C 4 -haloalkyl;

n 'is 0, 1,2 or 3, where (R ^l7) _n, is preferably 2,4-C1 _2;

R ¹⁸ is a radical of formula OR ²⁴ ;

R ²⁴ is hydrogen, (C ^ C ^ alkyl, (C ^ -CJhaloalkil, (C ^ -C ^ hydroxyalkyl, (C ₃ -C ₇₎ cycloalkyl, (C _| -C ₄₎ -alkoxy- (C ₁ -C ₄ -alkyl or tri-C 1 -C ₄ -alkylsilyl, preferably (C 1 -C ₄ ) alkyl;

R ²⁷ is hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₄ ) haloalkyl, or (C ₃ -C ₇ ) -cycloalkyl, preferably hydrogen or (C 1 -C ₄ ) -alkyl, and

R ²⁶ is hydrogen, (C 1 -C ₈ ) -alkyl, (C 1 -C ₄ ) haloalkyl, (C 1 -C ₄ ) -hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl or tri- (C 1 -C ₂ ) -alkylsilyl, preferably hydrogen or (C ₁ -C ₄ -alkyl).

Also particularly preferred are herbicidal compositions comprising an antidote of formula (II) in which the designations and indices have the following meanings:

W is (W 2);

R ¹⁷ is halogen or (C _| -C ₂₎ -haloalkyl;

n 'is 0, 1, 2 or 3, where (R ¹⁷ ) _n . is preferably 2,4-Cl ₂ ;

R ¹⁸ is a radical of formula OR ²⁴ ;

R ²⁴ is hydrogen, (C 1 -C 4 -alkyl, (C 1 -C ₄ ) haloalkyl, (C 1 -C 4 -hydroxyalkyl, (C ₃ -C)

65411 B1 cycloalkyl, (C 1 -C 4 -alkoxyC 1 -C 4 -alkyl or tri-C 1 -C 6 -alkylsilyl, preferably (C 1 -C 1 alkyl and

R ²⁷ is (C 1 -CJ-alkyl or (C 1 -CJ-haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl, preferably (C 1 -CJ-alkyl).

Also particularly preferred are herbicidal compositions comprising an antidote of formula (II) in which the designations and indices have the following meanings:

W is (W3);

R ¹⁷ is halogen or (C 1 -C 6 haloalkyl;

n 'is 0, 1, 2 or 3, where (R ¹⁷ ) _n . is preferably 2,4-Cl ₂ ;

R ¹⁸ is a radical of formula OR ²⁴ ;

R ²⁴ is hydrogen, (C 1 -CJ-alkyl, (C 1 -C ₄ ) haloalkyl, (C 1 -CJ-hydroxyalkyl, (C ₃ -C ₇ ) cycloalkyl, (C 1 -C 4 -alkoxy-C 1 -C 4 - alkyl or tri-C 1 -C 6 -alkylsilyl, preferably (C 1 -C 6 alkyl and

R ²⁸ is (C 1 -CJ-alkyl or (C 1 -CJ-haloalkyl, preferably C 1 -C 10 haloalkyl).

Particularly preferred are an antidote of formula (II) in which symbols and indices have the following meanings:

W is (W4);

R ¹⁷ is halogen, nitro, (C 1 -C ₄ ) -alkyl, (C 1 -C ₂ ) -haloalkyl, preferably CF ₃ or (C 1 -C ₄ ) -alkoxy, n 'is 0, 1, 2 or 3, t 'is 0 or 1,

R ¹⁸ is a radical of formula OR ²⁴ ;

R ²⁴ is hydrogen, (C 1 -C ₄ ) -alkyl, carboxy (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxycarbonyl- (C 1 -C ₁ alkyl), preferably (C 1 -C 3 -COCKCH) ) CO-CH ₂ , (C 1 -C ₄ ) -anKOKCH-CO-C (CH ₃ ) (H) -, HO-CO-CH ₂ or HO-CO-C (CH ₃ ) (H) -, and

R ²⁹ is hydrogen, (C 1 -CJ-alkyl, (C 1 -C ₄ ) haloalkyl, (C ₃ -C ₇ ) -cycloalkyl or phenyl which is unsubstituted or substituted by one or more halogen selected groups, (Cj -CJ-alkyl, (C1-CJ-haloalkyl, nitro group, cyano group and (C1-CJ alkoxy).

The following groups of compounds are particularly suitable for use as antidotes for herbicidally active substances of formula (I):

a) Dichlorophenylpyrazoline-

3-carboxylic acid type (i.e. of the formula (II), where W = (W1) and (R ¹⁷⁾ _n, = 2,4-ClJ, preferably compounds such as ethyl 1- (2,4-dichlorophenyl )

5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylate (II-1) and related compounds as described in WO 1991/007874;

b) dichlorophenylpyrazolecarboxylic acid derivatives (i.e., formula (II) in which W = (W 2) and (R ¹⁷ ) _n , = 2,4-Cl ₂ ), preferably compounds such as ethyl 1- (2, 4-dichlorophenyl) 5-methyl-pyrazole-3-carboxylate (II-2), ethyl 1 (2,4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate (II-2), ethyl 1- (2,4- dichlorophenyl) -5 (1,1-dimethylethyl) pyrazole-3-carboxylate (II-4), ethyl 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3carboxylate (II-5), related compounds as described in EP -A-0-3 33131 and EP-A-0269806;

c) compounds of the triazolecarboxyl type (i.e. formula (II), in which W = (W 3) and (R ¹⁷ ) _n , = 2,

4-Cl ₂ ), preferably compounds such as fenchlorazole ethyl, i. ethyl 1- (2,4-dichlorophenyl) -5trichloromethyl- (l) -1,2,4-triazole-3-carboxylate (II-6); fenchlorazole, i. e. 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 ') -1,2,4-triazole-3-carboxylic acid, and similar compounds (see EP-A-0 174 562 and EP-A-0 346 620);

d) compounds of the type 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid or the type 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (in which W = (W 4) 1, preferably compounds such as ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (II-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (II-8) and related compounds as described in WO 1991 / 008202, or ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (II-9), or

5,5-diphenyl-2-isoxazoline-3-carboxylic acid or η-propyl 5,5-diphenyl-2-isoxazoline-carboxylate (II-10) or ethyl 5- (4fluorophenyl) -5-phenyl-2-isoxazoline -3-carboxylate (11-11) as described in WO 1995/007897;

e) compounds of the type 8-quinolinoxyacetic acid, for example those of formula (III), in which (R ' ⁹ ) n. = 5-Cl, R ²⁰ = OR ²⁴ and T = CH 2, preferably compounds

-methyl (5-chloro-8-quinolinoxy) acetate (III-1),

1,3-dimethyl-but-1-yl (5-chloro-8-quinolinoxy) acetate (III-2),

4-alkyloxybutyl (5-chloro-8-quinolinoxy) acetate (III-3),

-allyloxyprop-2-yl (5-chloro-8-quinol

65411 Bnoxy) acetate (4-4), ethyl (5-chloro-8-quinolinoxy) acetate (1-5), methyl (5-chloro-8-quinolinoxy) acetate (1-6), allyl (5-chloro) -8-quinolinoxy) acetate (W-7),

2- (2-propylideneiminoxy) -1-ethyl (5-chloro-8-quinolinoxy) acetate (1H-8),

2- oxo-prop-1-yl (5-chloro-8-quinolinoxy) acetate (1H-9), and related compounds as described in EP-A-0 860 750, EP-A-0 094 349 and EP -A-0 191 736 or EP-A-0 492 366;

f) (5-Chloro-8-quinolinoxy) malonic acid type compounds, i. of formula (III) in which (R ¹⁹ ) '= 5-Cl, R ²⁰ = OR ²⁴ and T = -CH (COO-alkyl) -, preferably the compounds diethyl (5-chloro-8-quinolinoxy) malonate , diallyl (5-chloro-8-quinolinoxy) malonate, methyl ethyl (5-chloro-8-quinolinoxy) malonate and related compounds as described in EP-A-0 582 198;

g) compounds selected from:

4-dichloroacetyl-3,4-dihydro-3-methyl2H-1,4-benzoxacin (benoxacor, from EP 0 149 974),

3- dichloroacetyl-5- (2-furanyl) -2,2-dimethyloxazolidine (furylazole, MON 13900),

4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole),

B4- (4-methylphenyl) -N- (1-methyl-1-phenylethyl) urea (dymuron),

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea,

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylcarbamide,

1- [4- (L1-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea,

1- [4- (N-naphthoylsulfamoyl) phenyl] -3,3 dimethylcarbamide, (2,4-dichlorophenoxy) acetic acid (2,4-D); or (4-chlorophenoxy) acetic acid, (P, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),

4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA),

4- (4-chloro-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid,

3,6-dichloro-2-methoxybenzoic acid (dicamba),

- (ethoxycarbonyl) ethyl-3,6-dichloro-2-methoxybenzoate (lactidichloro), and their salts and esters, preferably (C 1 -C ₈ ); or

N- (4-chlorophenyl) maleimide (CMPI),

4-hydroxy-1-methyl-3- (1 -1 H-tetrazol-5-ylmethanoyl-1 H-quinolin-2-one, (S) -1- (1-alpha-butylbenzyl) -3-p-tolylcarbamide (( S) -MBU), and

5- 1-Methyl-1-phenylethyl piperidine-1-carbothioate (dimepiperate).

Also preferred as the antidote are the compounds of formula (IV) or salts thereof in which:

R ³⁰ is hydrogen; or R ³⁰ is (C 1 -C ₆ ) -alkyl, (C 1 -C ₆ -cycloalkyl, furanyl or thienyl, which radicals are unsubstituted or substituted by one or more halogen selected groups, (C 1 -C ₄ ) alkoxy , halo- (C (-C ₆ ) -alkoxy, and (C 1 -C ₆ alkylthio; and in the case of cyclic radicals, also (C 1 -C ₆ -alkyl, and (C 1 -C ₄ ) -haloalkyl,

R ³¹ is hydrogen,

R ³² is halogen, halo o- (C 1 -CJ-alkyl, halo (C 1 -CJ-alkoxy, (C ₁ -C 3 -alkyl), (C ₍ -C ₁ -C-alkoxy, (C 1 -C ₄ ) -alkylsulfonyl, ( C ^ CJ-alkoxycarbonyl, or (Cj-CJ-alkylcarbonyl, preferably halogen, (C _| -C ₄₎ -haloalkyl, such as trifluoromethyl, (C ^ CJ-alkoxy, halo- (C, -CJ-alkoxy, (Cj -C 1 -alkoxycarbonyl or (C 1 -C 6 alkylsulfonyl,

R ³³ is hydrogen,

R ³⁴ is halogen, (C 1 -C 1 -alkyl, halo- (C 1 -C ₄ ) alkyl, halo- N -C 1 -alkoxy, (C ₃ -C ₆ ) -cycloalkyl, phenyl, (C ₁ -C ₄ ) ₄₎ -alkoxy, cyano, (Cj-C ₄₎ -alkylthio, (C ₁ -C ₄₎ alkylsulfinyl, (Cj-CJalkilsulfonil, (Cj-CJ-alkoxy, or (C _{| -C4)} -alkylcarbonyl, preferably halogen, (C ^ CJ-alkyl, (C ^ CJ-haloalkyl, such as trifluoromethyl, hal o- (C ^ CJ-alkoxy, (C -CJalkoksi or (C] _-C4) -alkylthio, η 0 , 1 or 2 and t is 1 or 2.

Furthermore, an antidote of formula (V) is preferred in which

65411 Bl

X ³ eCH;

R ³⁵ is hydrogen; or R ³⁵ is (C 1 -C ₆ ) -alkyl, (C ₃ C ₆ ) -cycloalkyl, (C ₂ -C ₆ ) -alkenyl, (C ₅ -C ₆ ) cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl having up to three heteroatoms in the group selected from nitrogen, oxygen or sulfur, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, (C 1 -C ₆ ) - alkoxy, (C 1 -C 4 -haloalkoxy, (C 1 -C ₂ ) -alkylsulfinyl, (C ₁ -C ₂ ) -alkylsulfonyl, (C 1 -C ₆ ) -cycloalkyl, (C 1 -C ₄ ) -alkoxycarbonyl, (C 1 -C 4 -alkylcarbonyl and phenyl, and in the case of cyclic radicals also (C 1 -C 4 -alkyl and (C 1 -C 6 -haloalkyl,

R ³⁶ is hydrogen; or R ³⁶ is (C ₁ -C ₆ ) -alkyl, (C ₂ C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, hydroxide, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C 1 -C 4 -alkylthio);

R ³⁷ is halogen, (C ₁ -C ₄ ) -haloalkyl, (C 1 -C ₄ ) haloalkoxy, nitro, (C ₍ -C ₄ ) -alkyl, (C 1 -C ₄ ) alkoxy, (C ₁ - C ₄ -alkylsulfonyl (C 1 -C ₆ -alkoxycarbonyl or (C 1 -C ₄ ) -alkylcarbonyl;

R ³⁸ is hydrogen;

R ³⁹ is halogen, nitro, (C 1 -C ₄ ) -alkyl, (C 1 -C ₆ -haloalkyl, (C ₁ -C ₄ ) -haloalkoxy, (C ₃ -C ₆ ) cycloalkyl, phenyl, (C] -C ₄₎ -alkoxy, cyano, (C ₁ -C ₄₎ -alkylthio, (C _| -C ₄₎ alkylsulfinyl, (C] -C ₄₎ -alkylsulfonyl, (C ^ C ^ -alkoxycarbonyl or (C ₍ -C ₄ ) -alkylcarbonyl;

S is 0, 1 or 2, and o is 1 or 2.

The following subgroups are particularly preferred among the antidotes of formula (VI):

Compounds in which R ⁴⁸ and R ⁴⁹ are hydrogen, (C 1 -C 4 -alkyl, phenyl, phenyl- (C 1 -C ₈ ) -alkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₈ ) -alkyl , (C ₃ -C ₆ ) -alkenyl or (C ₃ -C ₆ ) -alkynyl, it is possible for the phenyl rings to be substituted by F, Cl, Br, NO ₂ , CN, OCH ₃ , (C 1 -C ₄ ) - alkyl or CH ₃ -SO ₂ ;

- Compounds in which R ⁹ is hydrogen;

- Compounds in which V is YR ^h ;

- Compounds in which E is oxygen;

- Compounds in which Q ¹ is CR ₂ ⁴⁷ ;

- Compounds in which R ⁴⁷ is hydrogen;

- Compounds in which m ”= 1 and E is oxygen or sulfur;

- Compounds in which w ”= 0;

- Compounds in which R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ and

R ⁴⁴ is in each case hydrogen, E is oxygen, Q ¹ is CR ⁴⁷ , V is YR ^h and w '= 1, especially those in which R ⁴⁷ is hydrogen, R ^b is CH ₃ , and Y is oxygen;

- Compounds in which Q is CR / ⁷ and m 'is 0, especially those in which R ⁴⁴ and R ⁴⁷ are hydrogen and V is YR ^h , where R ^h is preferably methyl and Y is preferably oxygen.

Most preferred are flurazole, which is benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate; fenchlorazole-ethyl, which is ethyl 1- (2,4-dichlorophenyl) -5trifluoromethyl-1 N-1,2,4-triazole-3-carboxylate; fenchlorazole, which is 1- (2,4-dichlorophenyl) -5-trifluoromethyl-l -1,2,4-triazole-3-carboxylic acid; enoxacor, which is (±) -4dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4benzoxacin; dichloromide, which is Ν, Ν-diallyl-

2,2-dichloroacetamide; fenclorim, which is 4,6dichloro-2-phenypyrimidine, furylazole, which (E5) -3-dichloroacetyl-5- (2-furyl) -2,2 dimethyloxazolidine; mefenpurdiethyl, which is diethyl (RS) -1- (2,4-dichlorophenyl) -5-methyl-2-pyrazoline-3,5-dicarboxylate; CMPI, which is N (4-chlorophenyl) maleic acid imide; 4-hydroxy-1-methyl-3- (1 -1H-tetrazol-5-ylmethanoyl) -1H-quinolin-2-one; daimuron which is 1- (1methyl-1-phenylethyl) -3-p-tolylcarbamide; (S) MBU, which is (S) -1- (1-alpha-methylbenzyl) -3-phtolylurea; demipiperate, which is S-1-methyl-

1-phenylethyl piperidine-1-carbothioate; 5,5-diphenylisoxazoline-3-carboxylic acid; and ethyl

5,5-diphenylisoxazoline-3-carboxylate (more preferably fenchlorazole; CMPI; 4-hydroxy-1-methyl-3- (1 -1H-tetrazol-5-ylmethanoyl) 1H-quinolin-2-one; (S) -MBU and dimepiperate).

The mixtures according to the present invention can be used to achieve selective control of weeds with little crop damage to various plants such as maize, soybean, cotton, canola, sugar beet, potatoes, wheat, tobacco, rice and rapeseed . Preferred crops include maize, sugar beet, cotton and canola. Maize and soybeans, especially maize, are particularly preferred crop types.

Effective weed control associated with low crop damage results from the treatment of the sowing area with a combination of herbicide derived from benzolisoxazole

65411 B1 and / or dione and an antidote compound according to the method of the present invention. Applying to a "plant site" means applying, for example, to a plant's growing medium, such as soil, as well as to seeds, sprouting seeds, roots, stems, leaves or other parts of plants.

The expression "combination of a herbicide derivative of isoxazole and / or dione and an antidote compound" includes various methods of treatment. For example, the soil at the plant site may be treated with a "tank mix" composition comprising a mixture of herbicide and antidote that is "in combination", or the soil may be treated with herbicides and antidote compounds separately such that "the combination "Can be prepared or obtained in the soil. After such treatments of the soil with a mixture of herbicide and antidote or individually or sequentially applying the herbicide and antidote to the soil, the herbicide and antidote can be mixed or introduced into the soil either by mechanical mixing of the soil with the additives or by "watering in" by spraying with rain gear or by watering. The soil at the plant site can also be treated with an antidote by administering the antidote in the form of a dispersible concentrate such as granulate. The granulate can be applied to the groove that is prepared to absorb the seeds of the crop and the herbicide can be applied to the crop site both before and after insertion into the groove of the pellet containing the antidote so that the herbicide and the antidote form a "combination" . Sowing seeds may be treated or coated with an antidote compound, or when sowing seeds are in the groove immediately after sowing, or more often, sowing seeds may be treated or covered before sowing in the groove. The herbicide can be applied to the soil culture well before or after planting, and a "combination" occurs when the seeds are covered by both the herbicide and the soil antidote.

In a preferred method according to the present invention (a) the benzoylisoxazole and / or dione herbicidal derivative and (b) the antidote are applied separately so that the antidote contacts the seeds or plant treated before the herbicidal compound. Separate application can be done, for example, by coating the seeds with an antidote. The seeds can be treated, for example, during sowing, for example by applying an antidote to the seeds or to the seed furrow or in the growing medium (eg soil), which then covers the seeds. The herbicidal agent may then be applied to the surface of the growing medium (e.g. soil) or to the soil layer above the layer containing the antidote.

Suitable seed sowing equipment, for example in furrows, are generally known in the art and applying an antidote to the soil layer to cover the seeds. The herbicide can then be applied to the soil surface, for example by spreading a fluid application form or distributing a solid application form.

Separate administration can also be accomplished, for example, by administering the herbicide compound and the antidote at the same time, preferably in a separate composition, which composition allows the antidote to be contacted with the seed or plant prior to contacting the herbicide compound.

For example, the composition may include a formulation for delayed release of the herbicidal compound such as, for example, the antidote of the composition to be released almost immediately and before the delayed release of the herbicidal compound. In one embodiment, the method of the present invention is preferably accomplished by applying an antidote directly to the seeds before sowing. This is usually done as a certain amount of seeds are sown with an antidote and then the seeds are sown.

In another preferred embodiment of the method according to the present invention, the antidote is selected from fenchlorazole; CMPI, 4-hydroxy-1-methyl-3- (1 -1H-tetrazol-5-ylmethanoyl) -1Hquinolin-2-one; (S) -MBU and dimepiperate.

The amount of a certain herbicide benzoylisoxazole and / or dione to be applied to the plant site or seed area depends on the nature of the weeds, the specific herbicide used,

65411 Bl application, climate and nature of culture. Application rates of about 0.004 kg / ha to 5 kg / ha of herbicide are generally suitable, preferably amounts of about 0.01 to 2 kg / ha and most preferably amounts of 0.005 to 0.3 kg / ha.

The amount of antidote used according to the method of the present invention varies according to a variety of parameters, including the antidote used, the crop protected, the amount and stages of the herbicide applied, and the prevailing climatic conditions. Also, the choice of an antidote for use according to the method of the present invention, the way in which it will be administered, and the determination of an action that is non-phytotoxic but antidotally effective, can be readily accomplished according to general practice in the art.

The antidote is administered in combination with the herbicide in a non-phytotoxic antidote effective amount. "Non-phytotoxic" means an amount of an antidote that causes little or no damage to the desired crop type. "Antidote-effective" means an antidote used in an amount that is effective as an antidote with a herbicide to reduce the degree of damage to the desired crop type caused by the herbicide.

The herbicide / safener combination of the present invention can also be used to control harmful plants in crop cultures of genetically engineered plants that are either known or still in the implementation stage. Typically, transgenic plants are characterized by particular, improved properties, such as resistance to certain plant protection products, resistance to plant diseases or pathogenicity causing plant diseases such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate to, for example, harvested in terms of quantity, quality, storage properties, composition and specific ingredients. Transgenic plants are known to have increased starch content or altered starch quality or the harvest they have has a different fatty acid composition.

Combinations of the present invention are used in economically important transgenic crops of useful plants or ornamental species, such as cereals such as wheat, barley, rye, oats, Italian millet, rice, cassava and maize and other crops such as sugar beet, cotton, soybean, oilseed rape, tomatoes, peas and other vegetables.

When the combinations of the present invention are applied to transgenic crops, the observed effects of harmful plants with respect to other crops are often accompanied by effects that are specific to the application of said transgenic crop, such as altered or specifically expanded spectrum of weeds that can be controlled , modified application rates that can be used, preferably good compatibility with the herbicides to which the transgenic crop is resistant, and altered growth and yield ansgennite crops.

Therefore, the invention also relates to the use of a combination of the present invention for controlling harmful plants in transgenic crops.

The following examples illustrate the present invention without limiting it, wherein antidote A is ethyl 5,5-diphenylisoxazoline-3-carboxylate and antidote B is 5,5-diphenylisoxazoline-3-carboxylic acid.

Example 1.

Corn seeds are sown in a non-sterile clay loess and a protective agent dissolved in acetone is added to the soil surface. After 30 minutes, a herbicide was treated with compound - A [5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzoyl) isoxazole] was applied to the treated soil.

days after treatment (DAT), a visual assessment of the percentage of phytotoxicity (measured as a decrease in green plant material or plant height) compared to the untreated control was performed.

Corn seeds are sown in non-sterile clay loess and grow to 1.5-2 leaves. An antidote dissolved in acetone is applied after germination to the soil surface. After 30 minutes treatment with herbicide - compound A [5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzene) was applied to the treated soil.

65411 B1 isoyl) isoxazole]. a visual assessment of the percentage of phytotoxicity14 days after treatment (DAT) was achieved when compared with the untreated control.

Activity of compound A prior to emergence of maize in the presence of an antidote

antidote g / hectare % phytotoxicity Compound A 63 15 System A + mefenp and p-diets l 63 8.75 S-we A + fenchlorazole-ethyl 63 11.3 C-we A + antidote A 63 11.3 C-we A + antidote B 63 8.75

Activity of compound A (63 g / ha) after emergence of maize in the presence of antidote

antidotes g / hectare % phytotoxicity Compound A 63 27.5 C-A + mefenpyr-diethyl 63 25 S-we A + fenchlorazole-ethyl 63 27.5 C-we A + antidote A 63 5 C-we A + antidote B 63 5

Activity of compound A (125 g / ha) after emergence of maize in the presence of antidote

antidote g / hectare % phytotoxicity Compound A 125 43 Compound A- + antidote A 31 15 Compound A + antidote A 63 10 Compound A + antidote A 125 15 Compound A + antidote B 31 19 Compound A + antidote B 63 18 Compound A + antidote B 125 25

a a

65411 Bl

The present invention also relates to herbicidal compositions comprising:

a) a herbicidally effective amount of a benzoylisoxazole and / or dione derivative of formula (I) or an agro-culturally acceptable salt or metal complex thereof; and

b) an effective amount of an antidote of or an agriculturally acceptable salt thereof;

preferably homogeneously dispersed in one or more compatible herbicidally acceptable diluents or carriers, or surfactants of a type generally acceptable in the art as suitable for use in herbicidal compositions and which are compatible with the herbicides of the present invention. In preferred compositions, the antidote contacts the seeds or plants that have previously been treated with the herbicidal compound. For example, the herbicidal compound may be in a delayed release formulation. The term "homogeneously dispersed" is used to include compositions wherein benzoylisoxazole and / or a dione of formula (I) and an antidote are dissolved in other components. The term "herbicidal composition" is used in a broad sense and includes not only compositions that are readily used as herbicides, but also concentrates that must be diluted before use. The herbicide to antidote ratio may vary depending on the crop being protected, the weeds being inhibited, the herbicide used, etc., but a herbicide to antidote ratio can generally be used in the range of 1:25 to 60: 1 wt. . hours, although the portion of the antidote used may be much larger, for example 1: 100 to 1: 300 wt. hours herbicide to antidote. The preferred ratio of herbicide to antidote is from 1:10 to 30: 1. Another preferred weight ratio is from 1: 1 to 20: 1, and even more preferred is a weight ratio of 2; 1 to 15: 1.

Preferably, the compositions contain from 0.05 to 90% by weight. benzoylisoxazole and / or dione of formula (I) and an antidote.

The herbicidal composition may contain solid or liquid carriers and surfactants (e.g. wetting agents, dispersants or emulsifiers alone or in combination). The surfactants that may be included in the herbicidal compositions of the present invention may be of ionic or nonionic type, such as sulforicinoleates, quaternary ammonium derivatives, ethylene oxide condensate products with nonyl or octylphenols, or carboxylic esters of anhydrosorbites which are soluble by the esterification of the three hydroxyl groups by condensation with ethylene oxide, alkali or alkaline earth metal salts of sulfuric acid esters and sulfonic Acids such as dinonyl and dioktilnatrivvi sulphonosuccinates and alkali and alkaline earth metals with sulfonic acid derivatives of high molecular weight such as sodium or calcium lignosulfonate. Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesium oxide, kieselguhr, tricalcium phosphate, powdered cork, carbon black and bentonite absorbent soot and clay. Examples of suitable liquid diluents include water, acetophenone, cyclohexanone, isophorone, toluene, xylene and mineral, animal and vegetable oils (these diluents can be used alone or in combination).

The herbicidal compositions of the present invention may also contain, if desired, suitable additives such as adhesives, protective colloids, sealants, penetrating agents, stabilizers, separators, anti-aggregates, colorants and corrosion inhibitors. These additives can also serve as diluents or carriers.

Granular administration forms can be prepared by absorbing the compounds of the present invention (dissolved in suitable solvents and, if desired, volatile) onto solid diluents or carriers in the form of granules, and if desired, evaporating the solvents or by granulating compositions in a powdery manner. species obtained as described above.

Powdery, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example, mineral or vegetable oils, in particular in the case of liquid concentrates in which the diluent or carrier is an oil to form compositions ready for

65411 Bl application.

Wetting powders (or spray powders) typically contain from 20 to 95% of the combination, and they typically contain, in addition to a solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersant, and if necessary from 0 up to 10% one or more stabilizers and / or other additives such as penetrating agents, adhesives or anti-sedimentation agents and colorants.

Concentrates in the form of aqueous suspensions, which are applied as a spray, are prepared in such a way that a stable fluid product (by fine grinding) is obtained which does not need to precipitate and they usually contain from 10 to 75% combination , from 0.5 to 15% surfactants, from 0.1 to 10% thixotropic agents, from 0 to 10% suitable additives such as antifoams, corrosion inhibitors, stabilizers and water or an organic liquid in which the active substance is moderately soluble or insoluble. Some organic solids or organic salts may be dissolved to help prevent precipitation or as antifreeze to water.

The application of a herbicide, antidote or mixtures thereof may be effected by conventionally used techniques such as manually portable or tractor mounted seed drills, powder spreaders, hand and sprayer systems, spray spreaders and pelletizing equipment. If desired, the application of the compositions of the present invention to the plants can be accomplished by introducing the compositions into the soil or other media. The herbicidal compositions of the present invention may comprise (a) and (b) linked to and preferably homogeneously dispersed in one or more compounds with pesticidal action and, if desired, one or more compatible pesticidally acceptable diluents or carriers. Examples of other pesticidal ingredients include fungicides, insecticides, plant growth regulators, and most preferably herbicides.

Optionally co-administered herbicides that can be combined with derivatives of formula (I) and an antidote are preferably selected from chloroacetamides (e.g., metalchlorine, acetochlor, alachlor), sulfonylureas, thiocarbamates, dithiocarbamates, metriblusumetramazine, metriblusumetramazine methyl, oxasulfuron, flumicolorac, bentazone, chlorimuron, linuron, clomozone, dimethenamide, pendimethalin, trifluralin, cletodim and acifpuorfen, bifenox, diflufenican, diuron, atrazine and ametrine.

According to another aspect, the present invention provides a product comprising:

(a) a herbicidally effective amount of a benzoylisoxazole and / or dione derivative of formula (I), or an agriculturally acceptable salt or metal complex thereof; and

B) an effective amount of an antidote compound or an agriculturally acceptable salt thereof;

as a combined preparation for separate, simultaneous or sequential application to control weeds at the crop site, the antidote being preferably in contact with the seeds or plants prior to the herbicidal compound.

Claims (13)

Claims 1. A method of reducing phytotoxicity to a single crop on site caused by the administration of benzoylisoxazole and / or a dione herbicide derivative of the formula wherein 65411 B1 (A-4) (A-5) R14e (A-7) or Formula (A-6a) or (A-7a), respectively; (A-6a) (A-7a) 65411B1 in which the positions of the carbonyl group and the Q group are reversed and the double bond in the ring is bonded to the carbon atom attached to the Q group; R is a hydrogen atom or a halogen atom; a straight- or branched-chain alkyl, alkenyl or alkynyl group containing from one to six carbon atoms which is optionally substituted by one or more halogen atoms; a cycloalkyl group containing from 3 to 6 carbon atoms, optionally substituted by one or more groups R ⁵ , one or more halogen atoms, or a group selected from -CO 2 R ³ , -COR ⁵ , cyano group, nitro group, -CONR ' R ⁴ , and -S (O) k R ¹³ ; R ¹ is a straight or branched chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms, optionally substituted by one or more groups R ⁵ or one or more halogen atoms; R ² is a halogen atom; a straight or branched chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; straight or branched chain alkyl group containing up to six carbon atoms which is substituted by one or more groups -OR ⁵ or a group selected from a nitro group, a cyano group, -CO 2 R ⁵ , -S (O) p R ⁶ , -O (CH2) mOR ^5, -COR ^5, -NRR ^12, -N (R ⁸⁾ SO2R ^7, -N (R ⁸⁾ CO2R ^7, -OR ^5, -OSO2R ^7, -SO2R ^7, -SO2NR ³ R ^4, -CONR'R ⁴ , -CSNR'R ⁴ , - (CR ⁸ R 10) y ^S (O) q R ⁷ and -SF 5; or two R ² groups of adjacent phenyl ring carbon atoms, together with the carbon atoms to which they are attached, may form a 5- to 7-membered saturated or unsaturated heterocyclic ring containing up to three ring heteroatoms selected from nitrogen, oxygen and sulfur, which ring is optionally substituted by one or more groups selected from halogen, nitro, -S (O) q, R ¹³ ; C, 4 alkyl, C, ₄ alkoxy, C] ₄ haloalkyl, C, ₄ haloalkoxy, = O (or 5 or 6-membered cyclic acetal thereof) and = NO-R ³ , it being understood that if a sulfur atom is present in the ring, it may be in the form of the group -SO- or -SO ₂ -; ζ is an integer from one to five; when ζ is greater than one, the groups R ² may be the same or different; R ³ , R ⁴ and R ^{10 are} each independently a hydrogen atom or a straight or branched chain alkali group containing up to six carbon atoms which are optionally substituted by one or more halogen atoms; R ⁵ and R ¹¹⁰ each independently are a straight or branched chain alkali group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms or an alkenyl or alkynyl straight or branched chain group containing two up to six (preferably three to six) carbon atoms, optionally substituted by one or more halogen atoms; R ⁶ and R ⁷ , which may be the same or different, are each R ⁵ ; or phenyl optionally substituted by one to five groups, which may be the same or different, selected from a halogen atom, a straight- or branched-chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms, a nitro group, a cyano group, -CO 2 R ⁵ , -S (O) p R ¹³ , -NR 'R ¹² , -OR ⁵ and -CONR'R ⁴ ; R ⁸ , R ⁹ and R ¹⁰ are each a hydrogen atom or R ⁶ , R ¹¹ and R ¹² are each a hydrogen atom or R ⁵ , R ¹³ and R ^{111 are} each a straight or branched chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; Q is a hydroxyl group, C _1-6 alkoxy, OR ² , SR ² or SR ¹¹¹ ; L is oxygen or NR ¹⁰⁹ , R ^14, R ^l4a, R ^14b, R ^{15, R 15a, R l5b, R} lb, R l6a, R 16b, rioo Rioi J ^ i02 R ¹⁰³ R ¹⁰⁴ R ¹⁰⁵ R ¹⁰⁶ R ¹⁰⁷ and R ¹⁰⁸ ca all the same or different groups selected from hydrogen, R ¹¹⁰ , - (CH ₂ ) _n CO ₂ R ¹⁰⁹ , halogen, cyano group, C] ₆ alkoxy, - (CH ₂ ) _x - [phenyl optionally substituted by one to five groups R ¹¹³ which may be the same or different] and cycloalkyl containing from three to six carbon atoms optionally substituted by C _{| 6} alkyl or -S (O) R ¹¹¹ ; R ¹¹² is phenyl optionally substituted by one to five groups selected from halogen, C, ₆ alkyl, C _I4j haloalkyl, C] _-C6 alkoxy and nitro; R ¹¹³ is a group selected from halogen, R ⁴ , nitro group, cyano group, -CO ₂ R ¹¹⁵ , -S (O) R ¹ , -OR ¹¹¹ and-NR ¹ R ⁵ R ¹¹⁶ ; 65411 Bl R ¹¹⁴ is a straight or branched chain alkyl group containing from one to three carbon atoms, optionally substituted by one or more halogen atoms; Rus _and R ¹¹⁶ , which may be the same or different, are each a hydrogen atom or R ¹⁰ ; p, q and and each independently are zero, one or two; whale each one is one, two or three; x is zero or one; y is an integer of one to four; when y is greater than one, the groups R ⁹ and R ¹⁰ may be the same or different; or an agriculturally acceptable salt or metal complex thereof; which method consists in that, preferably, before the herbicidal compound, an effective amount of an antidote compound and an optionally shared herbicide is applied to the crop site, wherein the antidote is selected from the group consisting of: a) compounds of formula (II) and (III) (I (ill) wherein n 'is an integer from zero to five, preferably from zero to three; T is a (C] or C ₂ ) alkanediyl chain which is unsubstituted or substituted by one or two C _1-6 alkyl radicals or by [(C ₃ C ₃ ) alkoxy] carbonyl; W is an unsubstituted or substituted divalent heterocyclic radical selected from the group of partially unsaturated or aromatic five membered heterocyclic rings having 1 to 3 N or O atoms in the ring, the ring having at least one N atom and no more than one O atom. preferably a radical selected from the group consisting of (W1) to (W4), COOR ”(W1) (W2) (W3) (W4) is zero or one; R ¹⁷ and R ¹⁹ are the same or different halogen, C _1-4 alkyl, C 1-4 ₄ alkoxy, nitro group, C ₁₄ haloalkyl; RU _and j220 _{are the same or} different OR ²⁴ , SR ²⁴ or NR ²⁴ R ²⁵ or a saturated or unsaturated 3 to 7 membered heterocycle having at least one N atom and up to three heteroatoms, preferably from the group selected from O and S which is different from the carbonyl group in (II) or (III) with respect to the N atom and is unsubstituted or substituted by radicals selected from the group consisting of (C 1 -C 4) alkyl, (C 1 -C 4) alkoxy or optionally substituted phenyl, preferably a radical of formula OR ²⁴ , NHR ²⁵ or N (CH 3) _2, and in particular of formula OR ²⁴ ; R ²⁴ is hydrogen or unsubstituted or substituted aliphatic hydrocarbon radical, preferably having from 1 to 18 C atoms in total; R ²⁵ is hydrogen, (C 1 -C 4 alkyl, (C 1 -C ₆ ) alkoxy or optionally substituted or unsubstituted phenyl; R ²⁶ is hydrogen, (C _{(C 8)} alkyl, (C] -C ₈₎ haloalkyl, (C ^ -C ^ alkoxy - ^ - C ^ alkyl, (C _t -C ₆₎ hydroxyalkyl, (C ₃ - C ₁₂ ) cycloalkyl or three (C ₍ -C ₄ ) alkylsilyl; and R ²⁷ , R ²⁸ , R ²⁹ are the same or different - hydrogen, (C 1 -C ₈ ) alkyl, (C ₍ -C ₈ ) haloalkyl, (C ₃ -C ₁₂ ) cycloalkyl or substituted or unsubstituted phenyl; B) one or more compounds selected from: 4,6-dichloro-2-phenylpyrimidine (fenclorin), benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole), N- (4-methylphenyl) -N '- (1-methyl-1-phenylethyl) urea (dymuron), 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methyl urea, 1- [4- (L1-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (1H-naphthoylsulfamoyl) phenyl] -3,3 dimethylurea; or (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-chlorophenoxy) acetic acid, N, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-Dichlorophenoxy) butyric acid 65411 B1 of (2,4-DB), (4-chloro-o-tolyloxy) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloro), and salts and esters thereof, preferably (C 1 -C ₈ ); or (±) -4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benzoxacor), (R) -3-dichloroacetyl-5- (2-furyl) -2,2 dimethyloxazolidine ( furylazole), N- (4-chlorophenyl) maleimide (CMPI), 4- hydroxy-1-methyl-3- (1 -1H-tetrazol-5ylmethanoyl) -1H-quinolin-2-one, (S) -1- (1-alpha-methylbenzyl) -3-p-tolylcarbamide ( (S) -MBU), and 5- 1-Methyl-1-phenylethyl piperidine-1-carbothioate (dimepiperate). c) N-acylsulfonamides of formula (IV) or salts thereof R ³⁰ is hydrogen; or R ³⁰ is a hydrocarbon radical, hydrocarbon oxy radical, hydrocarbon radical or heterocyclyl radical which is preferably bonded through a carbon atom, which radicals are unsubstituted or substituted by one or more groups selected from halogen, cyano, nitro , amino, hydroxyl, carboxyl, formyl, carboxamide, sulfonamide and radicals of the formula Z ^a -R ^a each hydrocarbon moiety preferably having 1 to 20 carbon atoms and a carbon radical R ^30, which covers the substituents preferably having 1 to 30 carbon atoms; R ³¹ is hydrogen or (C ₍ -C ₄ ) alkyl, preferably hydrogen, or R ³⁰ and R ³¹ together with the group of formula -CON- are a residue of a 3- to 8-membered saturated or unsaturated ring; R ³² is identical or different hydrogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH ₂ , SO ₂ NH ₂ or a radical of formula Z ^b- R ^b ; R ³³ is hydrogen or (C _{| -C4)} alkyl, preferably hydrogen; R ³⁴ is the same or different halogen, cyano group, nitro group, amino group, hydroxyl, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ or a radical of formula Z ^c- R ^c ; R ^a is a hydrocarbon radical or heterocyclyl radical, which radicals are unsubstituted or substituted by one or more groups, which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl, mono- and di- A C 1 -C 5 alkyl] amino or alkyl radical in which most preferably 2 or 3 non-adjacent CH ₂ groups are in each case substituted by one oxygen atom; R ^b and R ^c are the same or different hydrocarbon radical or heterocyclyl radical, which radicals are unsubstituted or substituted by one or more groups which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl , phosphoryl, halo- (C 1 -C ₄ ) alkoxy, mono- and di - [(C ₁ -C ₄ ) alkyl] amino, or alkyl radical, in which most preferably 2 or 3 non-adjacent CH ₂ groups in in each case are replaced by one oxygen atom; Z ^a is a bivalent group of formula O, S, CO, CS, CO-O, CO-S, O-CO, S-CO, SO, SO 2, NR *, CO-NR *, NR * -CO, SO 2 - NR * or NR * -SO2, the bond given on the right-hand side of each of the bivalent groups is the bond of the radical R ^a , and the radicals R * are each independently H, (C 1 -C 4) alkyl or halo ( C ₁ -C ₄ ) alkyl; Z ^b and Z ^c are each independently a direct bond or a bivalent group of formula O, S, CO, CS, CO-O, CO-S, O-CO, S-CO, SO, SO2, NR *, SO2 -NR *, NR * -SO2, CO-NR * or NR * -CO, where in the asymmetric bivalent groups the atom on the right side is attached to the radical R ^b or R ^c n, where the radicals R * are each independently H , (C 1 -C 4) alkyl or halo (C 1 -C ₄ ) alkyl; 65411 Bl Ο, 1 or 2, in particular 0 or 1, and t is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; d) acylsulfamoylbenzamides of formula (V) or salts thereof (V) wherein X ³ is CH or I; R ³⁵ is hydrogen or a heterocyclyl or hydrocarbon radical, the radicals of which are optionally substituted by one or more groups which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxide, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ and Z ^d -R ^d ; R ³⁶ is hydrogen, hydroxyl; or R ³⁶ is (C 1 -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) alkynyl, (C 1 -C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, which the radicals are optionally substituted by one or more groups, which may be the same or different, selected from halogen, hydroxyl group, C ₁₄ alkyl, C _1-4 alkoxy, C _{t 4} alkylthio, or R ³⁵ and R ³⁶ together with the nitrogen atom to which they are attached represent a 3- to 8-membered saturated or unsaturated ring; R ³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH ₂ , SO ₂ NH ₂ or Z'-R '; R ³⁸ is hydrogen, (C ₁ -C ₄ ) alkyl. (C ₂ -C ₄ ) alkenyl or (C ₂ -C ₄ ) alkynyl; R ³⁹ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO, CONH ₂ , SO ₂ NH ₂ or Z'-R '; R ^d is a (C 2 -C 20) -alkyl radical whose carbon chain is interrupted by one or more oxygen atoms; or R ^d is a heterocyclyl or hydrocarbon radical, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl, mono- and di - [(C C1-C4) alkyl] amino; R ^c and R ^f are the same or different (C ₂ -C ₂₀ ) alkyl radicals whose carbon chain is interrupted by one or more oxygen atoms; or R 'and R ^f are the same or different heterocyclyl or hydrocarbon radicals, which radicals are optionally substituted by one or more groups which may be the same or different, selected from halogen, cyano, nitro, amino, hydroxyl, phosphoryl , (C 1 -C ₄ ) haloalkoxy, mono- and di - [(C 1 -C ₄ ) alkyl] amino; Z ^d is a divalent unit selected from the group consisting of O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *, C (O) NR * or SO ₂ NR *; Z 'and Z ^f are the same or different and are a direct bond or a divalent radical selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR *, C (O ) NR * and SO ₂ NR *; R * is hydrogen, (C 1 -C ₄ ) -alkyl or (C 1 -C ₆ haloalkyl; s is an integer from 0 to 4, and o is an integer from 0 to 5 when X is CH, or is an integer from 0 to 4 when X is N; f) a compound of formula (VI) (VI) wherein R ⁴⁰ is hydrogen, (C 1 -C 6 -alkyl, (C 1 -C 4) alkyl substituted by (C 1 -C 4) -alkyl-X ⁴ or (C 1 -C 4) haloalkyl-X ⁴ , (C 1 -C 4) -haloalkyl, NO2, CN, -COO-R ⁴³ , NR2 ⁴⁴ , SO2NR2 ⁴⁵ or CONR2 ⁴⁶ ; R ⁴¹ is hydrogen, halogen, (C 1 -C ₄ ) -alkyl, CF ₃ , (C 1 -C ₄ ) alkoxy or (C ₁ -C ₄ ) -haloalkoxy; R ⁴² is hydrogen, halogen or (C ₍ -C ₄ ) -alkyl; Q ¹ , Q ² , E and G are the same or different O, S, CR, ⁴⁷ , CO, NR ₂ ⁴⁸ or a group of formula (VII) Rg Rg (VII) provided that 65411 B1 provided that (i) at least one of the group Q ¹ , Q ² , E, G is a carbonyl group, more specifically one of these groups is a radical of formula (VII) and that the group of formula (VII) is adjacent of the carbonyl group, and 5 (n) two adjacent groups Q ¹ , Q ² , E and G cannot be simultaneously oxygen; R ⁸ is the same or different hydrogen or (C 1 -C 8) -alkyl or the two R ⁸ radicals together are (C 2 -C ₆ ) -alkylene; 10 V is Y ³ -R ^h or NR ₂ ⁴⁹ ; X ⁴ is O or S (O) p Y ³ is O or S; R ^h is hydrogen, (C ₁ -C ₈ ) -alkyl, (C 1 -C 8) haloalkyl, (C ₍ -C ₄ ) -alkoxy- (C ₁ -C ₈ ) -alkyl, (C ₃ -C ₆ ) 15 -alkenyloxy-C ₁ -C 4 -alkyl or phenyl- (C ₁ -C ₈ ) -alkyl, wherein the phenyl ring is optionally substituted by halogen, (C 1 -C ₄ ) -alkyl, CF ₃ , methoxy or methyl- 8 (O) _x ; (C ₃ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) haloalkenyl, phenyl- (C ₃ -C ₆ ) -alkenyl, (C ₃ -C ₆ ) - 20 alkynyl, phenyl- (C ₃ -C ₆ ) -alkynyl, oxetanyl, furfuryl or tetrahydrofuryl; R ⁴³ is hydrogen or (C 1 -C ₄ ) -alkyl; R ⁴⁴ is hydrogen, (C 1 -C 4) -alkyl, (C 1 -C 4 -alkylcarbonyl or the two radicals R ⁴⁴ together are 25 (C 4 -C ₅ ) -alkylene; R ⁴⁵ and R ⁴⁶ are the same or different hydrogen, (C 1 -C 4) -alkyl, or the two radicals R ⁴⁵ and / or R ⁴⁶ together are (C 4 -C ₅ ) -alkylene, where a CH ₂ group may be substituted from O or S or one 30 or two CH ₂ groups may be substituted by NR ¹ ; R ¹ is hydrogen or (C 1 -C ₈ ) -alkyl; R ⁴⁷ is hydrogen, (C 1 -C 8) -alkyl or the two radicals R ⁴⁷ together are (C 2 -C ₆ ) -alkylene; 35 R ⁴⁸ is hydrogen, (C 1 -C ₈ ) -alkyl, substituted or unsubstituted phenyl, or benzyl, which is unsubstituted or substituted on the phenyl ring; R ⁴⁹ is hydrogen, (C 1 -C 8) -alkyl, phenyl, phenyl- (C 1 -C 8) -alkyl whose phenyl rings may be substituted by F, Cl, Br, NO 2, CN, OCH 3, ( C 1 -C 4) -alkyl or CH 3 SO 2 +; (C 1 -C 6 -alkoxy- (C 1 -C 8) -alkyl, (C 3 -C 6) -alkenyl, (C 3 -C 6) alkynyl, (C 3 -C 6) -cycloalkyl, or the two radicals R ⁴⁹ together are (C 4 -C) ₅ ) -alkylene, where one 45 CH ₂ group may be substituted by O or S or one or two CH ₂ groups may be substituted by NR ^k ; R ^k is hydrogen or (C 1 -C ₄ ) -alkyl; m * is 0 or 1 and 50 1 is 0, 1 or 2; including stereoisomers and agro-culturally acceptable salts. 2. The method of claim 1, wherein the herbicide isoxazole or dione has the general formula (Ia): wherein R is hydrogen or CO ₂ Et; R ¹¹⁷ is selected from -S (O) Me, Me, Et, chlorine, bromine or fluorine atom, methoxy, ethoxy and CH ₂ S (O) _q Me; R ¹¹⁸ is selected from a hydrogen atom, a chlorine, a bromine or a fluorine atom, methoxy, ethoxy and S (O) Me; R ¹¹⁹ is selected from hydrogen atom, chlorine, bromine or fluorine atom, methoxy and CF ₃ ; and p and q are each independently zero, one or two. The method of claim 1 or 2, wherein the herbicide isoxazole or dione has the general formula (Ib) wherein R ¹²⁰ is chlorine, bromine or trifluoromethyl; and R is hydrogen or -CO ₂ Et. The method of claim 1, wherein A in formula (I) is a group of formula o o o AAA H CN 65411 Bl The method of claim 4, wherein z is 2 and the groups R ₂ are independently selected from halogen, alkyl, S (O) _p alkyl (p = 0, 1 or 2) or haloalkyl. The method of claim 1, wherein 5 A is a group of formula The method of claim 1, wherein the compound of formula (1) is: 5-cyclopropyl-4- [2-chloro-3-ethoxy-4 (ethylsulfonyl) benzoyl] isoxazole; 4- (4-chloro-2-methylsulfonylbenzoyl) -5cyclopropyl-isoxazole; 5- cyclopropyl-4- (2-methylsulfonyl-4trifluoromethylbenzoyl) isoxazole; 4- (4-bromo-2-methylsulfonylbenzoyl) -5cyclopropyl-isoxazole; 5-cyclopropyl-4- [4-fluoro-3-methoxy-2 (methylsulfonyl) benzoyl] isoxazole; 4- (4-bromo-2-methylsulfonylmethylbenzoyl) -5-cyclopropyl-isoxazole; ethyl 5-cyclopropyl-4- (2-methylsulfonyl4-trifluoromethyl-benzoyl) isoxazole-3-carboxylate; 2- [2-chloro- (4-methylsulfonyl) benzoyl] -1- 3-cyclohexanedione; 2- [2-Nitro- (4-methylsulfonyl) benzoyl] -1- 3-cyclohexanedione; 2- (2,3-dihydro-5,8-dimethyl-1,1-dioxospiro [4H-1-benzothiine-4,2 '[1,3] dioxolane] -6 isoxazole; and 2-cyano-3-cyclopropyl-1- (2-methylsulfonyl-4-trifluoromethylphenyl) propane-1,3-dione. The method of claim 7, wherein the compound is 5-cyclopropyl-4- (2-methylsulfonyl-4-trifluoromethylbenzoyl) -isoxazole or 2- [2-nitro- (4-methylsulfonyl) benzoyl] -1,3-cyclohexanedione. The method of claim 1, wherein the antidote is selected from flurazole; fenchlorazolethyl; fenchlorazole; benzoxacor; fenclorim; furylazole; mefenpyr-diethyl; CMPI; 4-hydroxy-1-methyl-3- (1-1 H-tetrazol-5-ylmethanoyl) -1Hquinolin-2-one; dymuron; (S) -MBU; dimepiperate; 5,5-diphenylisoxazoline-3-carboxylic acid; and ethyl 5,5-diphenylisoxazoline-3-carboxylate. The method of claim 1, wherein the antidote is selected from fenchlorazole-ethyl; mefenpyr-diethyl; 5,5-diphenylisoxazoline-3-carboxylic acid; and ethyl 5,5-diphenylisoxazoline-3-carboxylate. A method according to any one of the preceding claims, wherein the crop crop is maize. The method of claim 1, wherein the amount of benzoyloxazole and / or dione of formula (I) administered is from 0.004 to 5 kg / ha. The method of claim 1, wherein the amount of benzoyloxazole and / or dione of formula (I) administered is from 0.01 to 2 kg / ha.