AU780137B2 - Combinations consisting of herbicides and safeners - Google Patents

Abstract

The invention relates to a herbicidally effective agent containing a mixture consisting of: (A) a herbicidally effective quantity of one or more compounds of formula (I), wherein R<1> represents hydrogen, C1-C4 alkyl, C3-C4 alkenyl, C3-C4 alkynyl C1-C4 haloalkyl; R<2> represents hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C6-C10 aryl, C6-C10 haloaryl, C1-C6 alkylsulfonyl-C1-C4 alkyl, di(C1-C6 alkyl)phosphono-C1-C4 alkyl, tri(C1-C6 alkyl)silyl-C1-C4 alkyl), C2-C7 alkanoyl-C1-C4 alkyl, carboxy-C1-C4 alkyl, (C1-C6 alkoxy)carbonyl-C1-C4 alkyl, {[C3-C9 ( alpha -alkylalkylidene)]iminooxy (C1-C6 alkoxy)carbonyl}-C1-C4 alkyl, (C3-C6 alkenyloxy)carbonyl-C1-C4 alkyl, (C3-C6 alkynyloxy)carbonyl- C1-C4 alkyl, (C3-C8 cycloalkyloxy)carbonyl-C1-C4 alkyl, phenoxy-C1-C4 alkyl, C3-C6 alkenyloxy-C1-C4 alkyl, C3-C8 cycloalkenyloxy-C1-C4 alkyl, C5-C8 cycloalkenyl, C6-C8 bicycloalkyl, C6-C8 bicycloalkenyl, C2-C7 cyanoalkyl or C3-C6 alkynyloxy-C1-C4 alkyl; R<3> represents hydrogen, halogen or cyano; R<4> represents hydrogen or halogen; R<5> represents hydrogen, halogen or C1-C4 alkyl, and; R<6> represents C1-C4 alkyl or C1-C4 haloalkyl, or together, R<5> and R<6> form trimethylene or tetramethylene, and the corresponding enol ethers of the compound of formula (I), wherein R<1> is different from hydrogen and C1-C4 haloalkyl, as well as the salts of the compound of formula (I), wherein, R<1> represents hydrogen, and of; (B) an antidotally effective quantity of one or more safeners.

Description

WO 01/08487 PCTIEPOO/07050 Combinations of herbicides and safeners The invention relates to the technical field of the crop protection products, in particular herbicide/antidote combinations (active substance/safener combinations) which are outstandingly suitable for the use against competing harmful plants in crops of useful plants.

EP-A 436 680 discloses herbicidal active substances which control a broad range of weeds and which, alone or as a mixture with other active substances, can be employed [lacuna] of important weeds; the publication not only describes what is known as the nonselective use jointly with nonselective foliar-acting herbicides, but also mentions the possibility of selective uses in crops which have been made tolerant to such active substances by recombinant methods.

However, many of these active substances are not fully compatible with not sufficiently selective in) some important crop plants such as maize, rice or cereals, so that their use is strictly limited. In certain crops, they can therefore not be employed, or at such low application rates that the desired broad herbicidal efficacy towards harmful plants is not guaranteed.

Specifically, many of the abovementioned herbicides cannot be employed sufficiently selectively against harmful plants in maize, rice, cereals or some other crops.

To overcome these disadvantages, it is known to employ herbicidal active substances in combination with a so-called safener or antidote. A safener for the purpose of the invention is a compound or a mixture of compounds which compensates for, or reduces, the phytotoxic properties of a herbicide towards useful plants without substantially reducing the herbicidal action against harmful plants.

The identification of a safener for a particular class of herbicides remains a difficult task since the exact mechanisms by which a safener reduces the harmful effect of herbicides are unknown. The fact that a compound in combination with a particular herbicide acts as a safener allows no conclusions as to whether such a compound also acts as a safener with other classes of herbicide. Thus, it has emerged that, when using safeners for protecting the useful plants from herbicide damage, the safeners may still have a number of disadvantages in many cases. These are: the safener reduces the action of the herbicides against the harmful plants, the useful-plant-protecting properties are insufficient, in combination with a given herbicide, the spectrum of the useful plants in which the safener/herbicide is to be used is insufficiently wide, a given safener may not be combined with a sufficiently large number of herbicides.

It was an object of the present invention to identify herbicidal compositions in which the selectivity of the abovementioned herbicides to important crop plants is increased. Surprisingly, this object is achieved by the herbicidal compositions of the present invention.

The invention therefore relates to comprising a mixture of a herbicidally effective amount formula (I) a herbicidally active composition of one or more compounds of the

COOR

2 in which

R

1 is hydrogen, C1-C4-alkyl, C3-C4-alkenyl, C3-C4-alkynyl or C1-C 4 haloalkyl, R is hydrogen, Ci-C10-alkyl, Ci-C10-haloalkyl, C6-C10-aryl, C6-C10-haloaryl, C1-C6-alkylsulfonyl-C1-C 4 -alkyl, di(C1-C 6 alkyl)phosphono-C 1 -C4-alkyl, tri(C1-C6-alkyl)silyl-C1-C4alkyl),

C

2

-C

7 -alkanoyl-C 1

-C

4 -alkyl, carboxy-Ci -C 4 -alkyl, (Ci -C 6 -alkoxy)carbonyl- Cl~-C 4 -alkyl, {[C 3 -C(ac-alkylalkylidene)]iminooxy-(C 1

-C

6 )-alkoxy)carbonyl}- Cl -C 4 -alkyl, (C 3

-C

6 -alkenyloxy)carbonyl-Ci -C 4 -alkyl, (03-06alkynyloxy)carbonyl-C 1

-C

4 -alkyl, (0 3

-C

8 -cycloalkyloxy)carbonyl-C 1 -0 4 -alkyl, phenoxy-C 1 -0 4 -alkyl, 0 3

-C

6 -alkenyloxy-C 1

-C

4 -alkyl, 0 3

-C

8 -cycloalkenyloxy- 01 -0 4 -alkyl, 0- 5 -0 8 -CYCloalkenyl, 0 6

-C

8 -bicycloal kyl, 0 6 -0 8 -bicycloalkenyl, 0 2

-C

7 -cyanoalkyl or 0 3 -0 6 -alkynyloxy-0 1 -0 4 -alkyl, R 3 is hydrogen, halogen or cyano, R 4 is hydrogen or halogen, R 5 is hydrogen, halogen or 0 1 -0 4 -alkyl, and R 6 is 0 1 -0 4 -alkyl or Cl-C 4 -haloalkyl, or R 5 and R 6 together form trimethylene or tetramethylene, and the corresponding eno! ethers of the compound of the formula in which R 1 is other than hydrogen and 0 1 -0 4 -haloalkyl, and the salts of the compound of the formula in which R 1 is hydrogen, and an antidote-effective amount of one or more safeners, wherein the safeners is/are preferably selected from the group consisting of compounds of the formulae (11) or (1ll), 0 (Rl 9 )n.

(R

1 7 )n.

T q, where the symbols and indices having the following meanings: n' is a natural number form 0 to 5, preferably 0 to 3; T is a (Cl or 0 2 )-alkanediyl chain which is unsubstituted or substituted by one or two (Cl-C 4 )alkyl radicals or by [(C 1

-C

3 )-alkoxy]carbonyl; W is an unsubstituted or substituted divalent heterocyclic radical selected from the group consisting of the partially unsaturated or aromatic fiveringed heterocycles having 1 to 3 hetero ring atoms of the type N or O, the ring containing at least one nitrogen atom and not more than one oxygen atom, preferably a radical selected from the group consisting of (W1) to (W4), N N NH2m N R 29 0-N

R

27

COOR

26

R

27 R 28 (W1) (W2) (W3) (W4) 10 m' is 0or1; i: 1

R

1

R

9 are identical or different halogen, (C 1

-C

4 )alkyl, (C 1 -C4)alkoxy, nitro or (C 1 -C4)haloalkyl;

R

1 8

R

20 are identical 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 nitrogen atom and up to 3 hetero atoms, preferably from the group consisting of O and S, which heterocycle is linked to the carbonyl group in (II) or (III) via the nitrogen atom and which is unsubstituted or substituted by radials selected from the group consisting of (C 1

-C

4 )alkyl, (C 1 -C4)alkoxy or optionally substituted phenyl, preferably a radical of the formula OR 24 20 NHR 25 or N(CH 3 2 in particular of the formula OR 24

R

24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms;

R

25 is hydrogen, (C 1

-C

6 )alkyl, (C 1

-C

6 )alkoxy or substituted or unsubstituted phenyl;

R

26 is hydrogen, (C 1

-C

8 )alkyl, (C 1

-C

8 )haolalkyl, (C 1

-C

4 )alkoxy-(C 1

-C

4 )alkyl, (C1- C6)hydroxyalkyl, (C3-C1 2 )cycloalkyl or tri-(C 1 -C4)-alkylsilyl;

R

27

R

28

R

29 are identical or different hydrogen, (C 1

-C

8 )alkyl, (C 1

-C

8 )haloalkyl,

(C

3

-C

12 )cycloalkyl or substituted or unsubstituted phenyl; inclusive of the stereoisomers and of the salts conventionally used in agriculture.

Examples of radicals R 2 are: acetylmethyl, 2-acetylethyl, prop ionylmethyl, cyanomethyl, trimethylsilylmethyl, 2- (trimethylsilyl) ethyl, 2-(methylsu If onyl) ethyl, methoxycarbo nyl methyl, eth oxyca rbonyl methyl, 1 -(methoxycarbonyl) ethyl, 1 (ethoxycarbo nyl) ethyl, 1 (ethoxycarbonyl)- 1 -methylethyl, 2-(ethoxycarbnoyl)- 1 -methylethyl, 1 (allyloxycarbonyl)-l1-methylethyl, isopropyl, 2-phenoxyethyl, 2-cyclohexenyl, 2cyanoethyl, 2-norbornanyl, 5-norbornen-2-yl, 2-allyloxyethyl and 2propargyloxyethyl.

If R 1 is C 3

-C

4 -alkenyl, C 3 -0 4 -alkynyl or C 1

-C

4 -haloalkyl, then allyl, propargyl and difluoromethyl are preferred in each case. If R 6 is Cl-C 4 -haloalkyl, then trifluoromethyl and pentafluoroethyl are preferred.

15 A preferred group of compounds of the formula are those in which R 2 is other than carboxy-0 1

-C

4 -alkyl, R 5 is hydrogen, fluorine or Cl-C 4 -alkyl and R 6 is C1rC4alkyl or Cl-0 4 -alkyl or C 1

-C

4 -haloalkyl, and their enol ethers and salts.

Also preferred are compounds of the formula in which

R

1 is Cl-C 4 -alkyl, preferable methyl, is C 2 -0 7 -alkanoyl-C 1 -0 4 -alkyl, (Cl -C 6 -alkoxy)carbonyl-C 1

-C

4 -alkyl, C1rC4alkyl, {[0 3

-C

9 )-(oa-alkylalkyl idene)iminooxy-(Ci -C 6 -alkoxy)-carbonyl]-0 1 -04alkyl, (0 3

-C

6 -alkenyloxy)carbonyl-0 1 -0 4 -alkyl, (0 3

-C

6 -alkynyloxy)carbonyl- Cl-C 4 -alkyl or (0 3

-C

8 -cycloalkyloxy)-carbonyl-Ci -0 4 -alkyl, *25 R 3 is halogen, preferably chlorine or bromine, or cyano, preferably chlorine, R 4 is hydrogen or fluorine, preferably hydrogen, R 5 is hydrogen, fluorine or methyl, preferably hydrogen, and R6 is methyl, trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl.

Preferred compounds of the formula are: ethyl 2-[2-chloro-5-[3,6-dihyd ro-3,4-dimethyl-2 ,6-dioxo- 1 (2H)-pyrimidinyl]-4f Iuo robe nzoyl oxy] -2-methyl propionate, methyl 2-{2-c hloro-5- [3,6-d ihyd ro-3,4-d im ethyl -2 ,6-d ioxo- 1 (2H)-pyrim idinyl]-4fluorobenzoyloxy}-2-methylpropionate, tert-butyl 2-{2-chloro-5-[3,6-dihydro-3,4-dimethyl-2,6-dioxo- 1 (2H)-pyrimidinyl]-4fluorobenzoyloxy}-2-methylpropionate, ethyl 2-ethyl -2-{2-chlIo ro-5-[3,6-d ihyd ro-3,4-d im ethyl -2,6-d ioxo- 1 (2H)-pyrimidinyl]- 4-f Iuorobenzoyloxylpropionate, methyl 2-{2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyrimidinyl]benzoyloxy}-2-methylpropionate, isopropyl 2-{2-ch lo ro-5-[3,6-d ihyd ro-2 ,6-d ioxo-3- methyl -4-triflIu oro methyl 1 (2H)pyrimidinyl]benzoyloxy~propionate, ethyl 2-ethyl-2-{2-chloro-5-[3,6-dihydro-2 ,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)-pyrimidinyl]benzoyloxylpropionate, tert-butyl 2-{2-chloro-5-[3,6-dihydro-2 ,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyri mid inyl]benzoyloxy)-2-methylpropionate, 15 allyl 2-{2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyrimidinyl]benzoyloxy)-2-methylpropionate, cyclopentyl 2-{2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethy- 1(2H)pyri mid inyllbenzoyloxy)-2-methylpropionate, ethyl 2-{2-chloro-5-[3,6-dihyd ro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyrimidinyl]benzoyloxylpropionate, ethyl 2-{2-chloro-5-[3,6-dihydro-2 ,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyrimidinyl]benzoyloxy}-2-methylpropionate, 1 -acetylethyl 2-chloro-5-[3,6-dihydro-2,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)- :pyrimidinyl]benzoate and, *25 ethyl 3-{2-chloro-5-[3,6-dihyd ro-2 ,6-dioxo-3-methyl-4-trifluoromethyl- 1 (2H)pyrimidinyl]benzoyloxylbenzoate.

Especially preferred compounds of the formula are butafenacil 1,1d imethyl -2-oxo-2- prope nyloxy) ethyl 2-ch lo ro-5 ,6-d ihyd ro-2,6-d ioxo-3- methyl- 4-trifluoromethyl-1 (2H)-pyrimidinyl]benzoate, GAS No.: 134 605-64-4) and flupropacil 1 -methylethyl 2-chloro-5-[3,6-dihydro-2 ,6-dioxo-3-methyl-4trifluoromethyl-l1-(2H)-pyrimidinyl]benzoate, UCC-C4243).

Herbicidally effective amount means, for the purposes of the invention, an amount of one or more herbicides which is suitable for adversely affecting plant growth.

Antidote-effective amount means, for the purposes of the invention, an amount of one or more safeners which is suitable for at least partially counteracting the phytotoxic effect of a herbicide or herbicide mixture on a useful plant.

Unless specifically defined otherwise, the following definitions generally apply to the radicals in formulae to (VIII) and the subsequent formulae.

0 0 *0 *o 9 9 9* 9.

9 *999 PAGES 8 TO 12 HAVE BEEN LEFT BLANK INTENTIONALLY EDITORIAL NOTE APPLICATION NUMBER 68271/00 This specification does not contain pages 9 to 12 The radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and/or substituted radicals in the carbon skeleton can each be straight-chain or branched.

Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl and the like, preferably have 1 to 4 carbon atoms and are, for example, methyl, ethyl, n- or i-propyl, t- or 2-butyl. Alkenyl and alkynyl radicals have the meaning of the unsaturated radicals which are possible and which correspond to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop- 2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-l-yl, but-3-en-l-yl, 1-methylbut- 3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl is, for example, propargyl, but- 2-in-1-yl, but-3-in-l-yl, 1-methylbut-3-in-1-yl. "(C1-C4)-Alkyl" is the abbreviation for alkyl having 1 to 4 carbon atoms; this also applies analogously to other general definitions of radicals whose ranges of the possible number of carbon atoms is given in brackets.

Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, especially preferably 3 to 6, carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl denote corresponding 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 by fluorine or chlorine, for example CF3, CHF 2 CH2F, CF 3

CF

2

CH

2 FCHCI, CCI 3 CHCI2, CH2CH 2 CI. Haloalkoxy is, for example, OCF3, OCHF2, OCH 2 F, CF3CF 2 0, OCH2CF3 and OCH2CH2CI. This also applies analogously to other halogen-substituted radicals.

A hydrocarbon radical can be an aromatic or an aliphatic hydrocarbon radical, an aliphatic hydrocarbon radical generally being a straight-chain or branched saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, especially preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl.

An aliphatic hydrocarbon radical preferably means alkyl, alkenyl or alkynyl having up to 12 carbon atoms; this also applies analogously to an aliphatic hydrocarbon radical in a hydrocarbonoxy radical.

Aryl is generally a mono-, bi- or polycyclic aromatic system having preferably 6-20 carbon atoms, by preference 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 denotes a mono-, bior polycyclic ring system which is saturated, unsaturated and/or aromatic and has one or more, preferably 1 to 4, hetero atoms, preferably selected from the group consisting of N, S and 0.

Preferred are saturated heterocycles having 3 to 7 ring atoms and one or two hetero atoms selected from the group consisting of N, O and S, chalcogens not being adjacent. Especially preferred are monocyclic rings having 3 to 7 ring atoms and one hetero atom selected from the group consisting of N, O and S, and also morpholine, dioxolane, piperazine, imidazoline and oxazolidine. Very especially preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.

Also preferred are partially unsaturated heterocycles having 5 to 7 ring atoms and one or two hetero atoms selected from the group consisting of N, O and S. Especially preferred are partially unsaturated heterocycles having 5 to 6 ring atoms and one hetero atom selected from the group consisting of N, O and S. Very especially preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline.

Also preferred is heteroaryl, e.g. mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms which contain one to four hetero atoms selected from the group consisting of N, O, S, chalcogens not being adjacent.

Especially preferred are monocyclic aromatic heterocycles having 5 to 6 ring atoms and containing a hetero atom selected from the group consisting of N, O and S, and also pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and isoxazole.

Very especially preferred are pyrazole, thiazole, triazole and furan.

Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl such as phenyl and arylalkyl such as benzyl, or substituted heterocyclyl, are a substituted radical derived from the unsubstituted skeleton, the substituents preferably being one or more, preferably 1, 2 or 3, in the case of CI and F also up to the maximum possible number of, substituents selected from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic substituents corresponding to the abovementioned saturated hydrocarbon-containing substituents, preferably alkenyl, alkynyl, alkenyloxy, alkynyloxy. In the case of radicals with carbon atoms, those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Preferred are, as a rule, substitutents selected from the group consisting of halogen, for example fluorine or chlorine, (C1-C4)alkyl, preferably methyl or ethyl, (C1-C 4 )haloalkyl, preferably trifluoromethyl, (C1-C4)alkoxy, preferably methoxy or ethoxy, (C1-C4)haloalkoxy, nitro and cyano. Especially preferred are the substituents methyl, methoxy and chlorine.

Mono- or disubstituted amino denotes a chemically stable radical selected from the group consisting of the substituted amino radicals which are Nsubstituted, for example, by one or two identical or different radicals selected from the group consisting of alkyl, alkoxy, acyl and aryl, preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles. Alkyl radicals having 1 to 4 carbon atoms are preferred. Aryl is preferably phenyl. Substituted aryl is in this case preferably substituted phenyl. As far as acyl is concerned, the definition given further below applies, preferably (C1-C4)alkanoyl. This also applies analogously to substituted hydroxylamino or hydrazino.

Optionally substituted phenyl is, preferably, phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, in the case of halogen such as Cl and F also up to pentasubstituted, by identical or different radicals selected from the group consisting of (C1-C4)alkyl, (C1-C 4 )alkoxy, (C1-C4)haloalkyl, (Cl-C 4 )haloalkoxy and nitro, for example m- and p-tolyl, dimethylphenyls, 3- and 4-chlorophenyl, 3- and 4-trifluoro- and -trichlorophenyl, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

An acyl radical denotes the radical of an organic acid preferably having up to 6 carbon atoms, for example the radical of a carboxylic acid and radicals of acids derived therefrom such as of thiocarboxylic acid, optionally Nsubstituted iminocarboxylic acids, or the radical of carbonic monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl is, for example, formyl, alkylcarbonyl such as (C1-C4-alkyl)carbonyl, phenylcarbonyl, it being possible for the phenyl ring to be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl or N-alkyl-1-iminoalkyl.

The formulae to (VIII) also encompass all stereoisomers whose atoms have the same topological linkage, and mixtures of these stereoisomers.

Such compounds contain one or more asymmetric carbon atoms or else double bonds which are not especially mentioned in the formulae. The possible stereoisomers which are defined by their specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers, may be obtained by customary methods from stereoisomer mixtures or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.

Herbicides of the formula are disclosed, for example, in EP-A-436 680, which contains extensive information on preparation processes and starting materials and mentions preferred compounds. This publication is referred to expressly and it is incorporated herein by reference. The compounds of the formula (II) are disclosed, for example, in EP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (US-A-4,891,057), EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0 346 620 (WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA 94/7120) and in the literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula (III) are disclosed in EP-A-0 086 750, EP-A-0 94349 (US-A-4,902,340), EP-A-0 191736 (US-A-4,881,966) and EP-A-0 492 366 and in the literature cited therein or can be prepared by or analogously to the processes described therein.

Some compounds are furthermore described in EP-A-0 582 198.

The compounds of the formula (IV) are disclosed in a large number of patent applications, for example US-A-4,021,224 and US-A-4,021,229.

Compounds of group B(b) are furthermore known from CN-A-87/102 789, EP-A-365484 and from "The Pesticide Manual", The British Crop Protection Council and the Royal Society of Chemistry, 11th edition, Farnham 1997.

The compounds of group B are described in WO-A-97/45016, those of group B in German Patent Application 197 42 951.3, and those of group B in WO-A 98/13 361.

The cited publications contain extensive information on preparation processes and starting materials and mention preferred compounds. These publications are referred to expressly and they are incorporated herein by reference.

Preferred herbicide/safener combinations are those which comprise safeners of the formula (II) and/or (III) in which the symbols and indices have the following meanings: R24 is hydrogen, (C1-C18)alkyl, (C 3

-C

12 )cycloalkyl, (C2-C8)alkenyl and (C2-C18)alkynyl, it being possible for the carbon-containing groups to be substituted by one or more, preferably up to three, radicals is identical or different halogen, hydroxyl, (Ci-C8)alkoxy, (C1-C8)alkylthio, (C 2

-C

8 )alkenylthio, (C2-C8)alkynylthio, (C2-C 8 alkenyloxy, (C2-C8)alkynyloxy, (C3-C7)cycloalkyl, (C3-C7)cycloalkoxy, cyano, mono- and di(C1l-C4)alkyl)amino, carboxyl, (C1 -C8)alkoxycarbonyl, (C2-C8)alkenyloxycarbonyl, (C1-C8)alkylthiocarbonyl, (C2-C8)alkynyloxycarbonyl, (C1 -C8)alkylcarbonyl, (C2-C8)alkenylcarbonyl, (C2-C8)alkynylcarbonyl, 1-(hydroxyimino)-

(C

1 -C6)alkyl, 1-[(C1 -C4)alkylimino](C1 -C4)alkyl, 1-[(C 1 -C4)alkoxyimino](C1-C 6 )alkyl, (C 1 -C8)alkylcarbonylamino, (C2-C8)alkenylcarbonylamino, (C2-C8)alkynylcarbonylamino, aminocarbonyl,

(C

1 -C8)alkylaminocarbonyl, di-(C1-C 6 )alkylaminocarbonyl, (C2-C 6 alkenylaminocarbonyl, (C2-C6)alkynylaminocarbonyl, (C1-C8)alkoxycarbonylamino, (C1 -C8)alkylaminocarbonylamino, (C1-C6)alkylcarbonyloxy, which is unsubstituted or substituted by R, (C2-C6)alkenylcarbonyloxy, (C2-C 6 )alkynylcarbonyloxy, (C1-C8)alkylsulfonyl, phenyl, phenyl(C1-C6)alkoxy, phenyl(Cl-C6)alkoxycarbonyl, phenoxy, phenoxy(C1 -C6)alkoxy, phenoxy(C 1 -C6)alkoxycarbonyl, phenylcarbonyloxy, phenylcarbonylamino, phenyl(C1-C6)alkylcarbonylamino, it being possible for the last-mentioned 9 radicals to be unsubstituted or mono- or polysubstituted in the phenyl ring, preferably up to trisubstituted, by radicals R52; SiR' 3 -O-SiR' 3 R'3Si-(C1-C 8 )alkoxy, -CO-O-NR' 2 -O-N=CR'2, -N=CR' 2 -O-NR'2, -NR' 2

CH(OR')

2 -O-(CH2)m-CH(OR')2, 2 -0- (CH2)mCR"'(OR")2 or by R"O-CHR"'CHCOR"-(C1-C 6 )alkoxy, R51 is identical or different halogen, nitro, (C1-C4)alkoxy and phenyl which is unsubstituted or substituted by one or more, preferably up to three, radicals R51 R52 is identical or different halogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)haloalkyl, (C1-C4)haloalkoxy or nitro; R' is identical or different hydrogen, (C1-C4)alkyl, phenyl which is unsubstituted or substituted by one or more, preferably up to three, 52 radicals R or two radicals R' together form a (C2-C6)alkanediyl chain; R" is identical or different (C1-C4)alkyl or two radicals R" together form a (C2-C6)alkanediyl chain; is hydrogen or (C1-C4)alkyl; m is 0, 1, 2, 3, 4, 5 or 6.

Especially preferred are herbicide/safener combinations according to the invention comprising safener of the formula (II) and/or (III) where the symbols and indices have the following meanings: 24 R is hydrogen, (C1-C8)alkyl or (C3-C7)cycloalkyl, the abovementioned carbon-containing radicals being unsubstituted or mono- or polysubstituted by halogen or mono- or disubstituted, preferably monosubstituted, by radicals R R50 is identical or different hydroxyl, (C1-C4)alkoxy, carboxyl, (C1 -C4)alkoxycarbonyl, (C2-C6)alkenyloxycarbonyl, (C2-C6)alkynyloxycarbonyl, 1-(hydroxyimino)(C1-C 4 )alkyl, 1-[(C1 -C4)alkylimino]- (C1-C 4 )alkyl and 1-[(C1 -C 4 )alkoxyimino](C1-C 4 )alkyl; -SiR' 3 -O-N=CR'2, -N=CR'2, -NR' 2 and -O-NR'2, in which R' is identical or different hydrogen, (C1-C4)alkyl or, as a pair, a chain, 27 28 29 R R R are identical or different hydrogen, (Cl-C8)alkyl, (Cl-C 6 )haloalkyl, (C3-C7)cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, amino, mono- and di[(Cl-C4)alkyl]amino, (Cl-C4)alkyl, (Cl-C 4 )haloalkyl, (Cl-C4)alkoxy, (Ci -C4)haloalkoxy, (C1-C4)alkylthio and (Cl-C4)alkylsulfonyl; R 26is hydrogen, (Ci -C8)alkyl, (Ci -C8)haloalkyl, (Ci -C4)alkoxy)(Cl -04)alkyl, (Ci -C6)hydroxyalkyl, (C3-C7)cycloalkyl or tri(Ci -C4)alkylsilyl, 17 19 R ,R are identical or different hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, (Ci or C2)haloalkyl, preferably hydrogen, halogen or (C 1 or C2)haloalkyl.

Very especially preferred safeners are those in which the symbols and indices in formula (11) have the following meanings: R 17is halogen, nitro or (Cl-C4)haloalkyl; n'6 is0, 1, 2or 3; 18 24 R is aradical of the formula OR R 24is hydrogen, (Cl-C8)alkyl or (C3-C7)cycloalkyl, the above carboncontaining radicals being unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different halogen radicals or up to disubstituted, preferably monosubstituted by identical or different radicals selected from the group consisting of hydroxyl, (Cl-C4)alkoxy, (C 1

-C

4 )alkoxycarbonyl, (C2-C6)alkenyloxycarbonyl, (C2-C6)alkynyloxycarbonyl, 1 -(hydroxyimino)(Cl-C4)alkyl, 1 1 -C4)alkylimino](Cl-C 4 )alkyl, 1 -C 4 )alkoxyimino](Ci -C 4 alkyl and radicals of the formulae -SiR' 3

-N=CR'

2 -NR'2 and -O-NR'2, the radicals R' in the abovementioned formulae being identical or different hydrogen, (Cl-C 4 )alkyl or, in pairs, (C4 or R 2, R 2, R 29are identical or different hydrogen, (Cl-C8)alkyl, (Ci -C6)haloalkyl, (C3-C7)cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (Cl-C4)alkyl, (Cl-C 4 )alkoxy, nitro, (Cl-C4)haloalkyl and (Cl-C4)haloalkoxy, and R 26is hydrogen, (Ci -C8)alkyl, (Cl-C8)haloalkyI, (Cl-C 4 )alkoxy-(Ci -C 4 alkyl, (Cl-C6)hydroxyalkyl, (C3-C7)cycloalkyl or tri(Ci -C4)alkylsilyl.

Very especially preferred safeners; are also those of the formula (1ll) in which the symbols and indices have the following meanings: R 19is halogen or (Cl-C4)haloalkyl; n6 is 0, 1, 2 or 3, where (R 19)n' is preferably R 20is aradical of the formula OR 2 T is OH 2 or CH(COO-(Cl-C3-alkyl)) and R 24is hydrogen, (Cl-C8)alkyl, (C1-C8)haloalkyl or (Cl-C4)alkoxy- (Cl-C4)alkyl, preferably (01-C8)alkyl.

Particularly preferred are the safeners of the formula (11) in which the symbols and indices have the following meanings: W is (W1); R 17is halogen or (Cl-02)haloalkyl; n'A is 0, 1, 2 or 3, (R 17)n' preferably being 2,4-C12; R 18is aradical of the formula OR 2 R 24is hydrogen, (Ci -C8)alkyl, (01-C4)haloalkyl, (Cl-C4)hydroxyalkyl, (C3-C7)cycloalkyl, (Cl-C4)alkoxy(C1 -C4)alkyl or tri(C1-C2)alkylsilyl, preferably (CI-C4)alkyl; R 27is hydrogen, (Cl-C8)alkyl, (Cl-04)haloalkyl or (C3-C7)cycloalkyl, preferably hydrogen or (Cl-C4)alkyl, and R 26is hydrogen, (Ci -C8)alkyl, (Ci-C4)haloalkyl, (Cl-C 4 )hydroxyalkyl, (C3-C7)cycloalkyl, (Cl-C4)alkoxy(Cl-C4)alkyl or tri(CI -C2)alkylsilyl, preferably hydrogen or (Cl-C4)alkyl.

Also particularly preferred are herbicidal compositions comprising a safener of the formula (11) where the symbols and indices have the following meanings: W is (W2); R 17is halogen or (Cl-C2)haloalkyl; n' is 0, 1, 2 or 3, (R 17)n' preferably being 2,4-C12; R 18is a radical of the formulaOR2 R 24is hydrogen, (Ci -08)alkyl, (Cl-C4)haloalkyl, (Cl-C4)hydroxyalkyl, (C3-C7)cycloal kyl, (Cii )lkxy-04-alkyl or tri(Cl1-C2)alkylsilyl, preferably (01-04)alkyl, and R 27is hydrogen, (Cl-C8)alkyl, (Cl-04)haloalkyl, (C3-C7)cycloalkyl or phenyl, preferably hydrogen or (Cl-04)alkyl.

Also particularly preferred are safeners of the formula (II) where the symbols and indices have the following meanings: W is (W3); 17 R is halogen or (C1-C2)haloalkyl; n' is 0, 1, 2 or 3, (R17 preferably being 2,4-012; 18 24 R is a radical of the formula OR24 R24 is hydrogen, (C1-C8)alkyl, (C 1

-C

4 )haloalkyl, (C1-C4)hydroxyalkyl, (C3-C7)cycloalkyl, (C1-C 4 )alkoxy(C1 -C 4 )alkyl or tri(C1-C2)alkylsilyl, preferably (C1-C4)alkyl, and R28 is (C1-C8)alkyl or (C 1

-C

4 )haloalkyl, preferably C1-haloalkyl.

Also particularly preferred are safeners of the formula (II) where the symbols and indices have the following meanings: W is (W4); 17 R17 is halogen, nitro, (C1-C4)alkyl, (C1-C2)haloalkyl, preferably CF3 or (C1-C 4 )alkoxy; n' is 0, 1, 2 or 3; m' is 0 or 1; R18 is a radical of the formula OR24 R24 is hydrogen, (C1-C4)alkyl, carboxy(C1 -C4)alkyl, (C1-C4)alkoxycarbonyl(C 1 -C4)alkyl, preferably (C1 -C 4 )alkoxy-CO-CH2-, (C1-C 4 )alkoxy-CO-C(CH3)H-, HO-CO-CH 2 or HO-CO-C(CH3)H-, and R29 is hydrogen, (C1-C4)alkyl, (C1-C 4 )haloalkyl, (C3-C7)cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1-C4)alkyl, (C1-C4)haloalkyl, nitro, cyano and (C 1

-C

4 )alkoxy.

The following groups of compounds are particularly suitable as safeners for the herbicidal active substances of the formula a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type 17 of the formula where W' W1 and (R17 2,4-012), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5- (ethoxycarbonyl)-5-methyl-2-pyrazoli ne-3-carboxylate (11-1, mefenpyr-diethyl), and related compounds as they are described in WO-A 91/07874; b) dichlorophenylpyrazolecarbox V ic acid derivatives of the formula where W (W2) and (R1 2,4-012), preferably compounds such as ethyl 1 ,4-d ich loro phenyl)-5-methyl pyrazole-3-carboxyl ate ethyl 1 ,4-dichlorophenyl )-5-isopropylpyrazole-3-carboxylate ethyl 1 -(2,4-dichlorophenyl)-5-(1 ,1 Adi methyl ethyl) pyrazol e-3carboxylate ethyl 1 -(2,4-dichlorophenyl)-5-phenylpyrazole-3carboxylate (11-5) and related compounds as they are described in EP-A-0 333 131 and EP-A-0 269 806.

c) Compounds of the triazolecarboxylic acid type of the formula where W (M3) and (R 17)n' 2,4-012), preferably compounds such as fenchlorazol-ethyl, i.e. ethyl 1-(2,4-dichlorophenyl)- 5-trichloromethyl-(1 H)-1 ,2,4-triazole-3-carboxylate and related compounds (see EP-A-0 174 562 and EP-A-0 346 620); d) compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid type or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (where W preferably compounds such as ethyl 5-(2 ,4-d ichlIo robe nzyl soxazol ine-3-ca rboxyl ate (11-7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (11-8) and related compounds as they are described in WO-A-91/08202, or of the ethyl 5 ,5-diphenyl-2-isoxazolinecarboxylate type (11-9, isoxadifen-ethyl), the n-propyl 5,5-d iphenyl-2-isoxazolinecarboxylate type (11-10) or the ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate type (1l-11), as they are described in WO-A-95/07897.

e) Compounds of the 8-quinolinoxyacetic acid type, for example those 1920 24 of the formula (1ll), where (R9)n =5-Cl, R =OR and T CH2, preferably the compounds 1 -methylhexyl (5-chloro-8-q uinolinoxy)acetate (1ll-1, cloqu intocetmexyl), 1 ,3-dimethylbut-1 -yl (5-chloro-8-quinolinoxy)acetate (111-2), 4-allyloxy-butyl (5-ch loro-8-quinolinoxy)acetate (111-3), 1 -allyloxyprop-2-yl (5-chloro-8-qu inolinoxy)acetate (11 1-4), ethyl (5-chloro-8-quinolinoxy)acetate (111-5), methyl (5-chloro-8-q uinolinoxy)acetate (111-6), allyl (5-chloro-8-quinolinoxy)acetate (111-7), 2-(2-propylideneiminoxy)- 1-ethyl (5-ch loro-8-qu inolinoxy)acetate (111-8), 2-oxoprop-1 -yl (5-chloro-8-qu inolinoxy)acetate (111-9) and related compounds as they are 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) Compounds of the (5-chloro-8-quinolinoxy)malonic acid type, i.e. of the formula (1ll), where (R 19)n' 5-C1, R 20= OR 2, T CH(COOalkyl)-, preferably the compounds diethyl (5-chloro-8quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate and related compounds as they are described in EP-A-0 582 198.

g) compounds of the dichloroacetamide type, i.e. of the formula (IV), preferably: N,N-diallyl-2,2-dichloroacetamide (dichlormid, disclosed in US-A 4,137,070), 4-d ichloroacetyl-3,4-d ihydro-3-methyl-2H-1 ,4-benzoxazine (IV-1, benoxacor, disclosed in EP 0 149 974), N 1,N -_diallyl-N -_dichloroacetylglycinamide (DKA-24, disclosed in HU 2143821), 4-d ichloroacetyl-1 -oxa-4-aza-spiro[4,5]decane (AD-67), 2,2-dichloro-N-(1 ,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1 292), 3-dichloroacetyl-2 ,2 3-d ichloroacetyl-2 3-dichloroacetyl-2 ,2-d imethyl-5-(2-thienyl)oxazol idime, 3-dichloroacetyl-5-(2-furanyl ,2-dimethyloxazolidime (furilazole, MON 13900), 1 -d ichloroacetyl hexahydro-3 ,3,8a-trimethylpyrrolo[1 ,2-a]pyrimidine- 6(2H)-one (dicyclonon, BAS 145138), h) compounds of group preferably 1 ,8-naphthalic anhydride, methyl diphenylmethoxyacetate, cyanomethoxyimino(phenyl)acetonitrile (cyometrinil), 1 ,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil), 4'-chloro-2,2,2-trifluoroacetophenone 0-1 ,3-dioxolan-2ylmethyloxime (fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl 2-chloro-4-trifluoromethyl-1 (flurazole), 2-d ichloromethyl-2-methyl-1 ,3-dioxolan (MG-i 91), N-(4-methylphenyl)-N'-(1-methyl-1-phenylethyl)urea (dymron), 1 -[4-(N-2-methoxybenzoylsulfa moyl)phenyl]-3-methylu rea, 1 -j4-(N-2-methoxybenzoylsu Ifamoyl )phenyl]-3,3-dimethylurea, 1 -[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyll-3-methylurea, 1 -[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, (2,4-dichlorophenoxy)acetic acid (h1-1, 2,4-D), (4-chlorophenoxy)acetic acid, S)-2-(4-ch loro-o-tolyloxy)pro pion ic acid (h1-2, 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 (dicamba), 1 -(ethoxycarbonyl)ethyl 3 ,6-d ichloro-2-methoxybenzoate (lactidichlor) and their salts and esters, preferably (0-08).

Furthermore preferred as safeners are compounds of the formula or their salts, where R 0is hydrogen, (Cl-C~)alkyl, (C3-C6)cycloalkyl, furanyl or thienyl, it being possible for each of the last-mentioned 4 radicals to be unsubstituted or substituted by one or more substituents selected from the group consisting of halogen, (Cl-C 4 )alkoxy, halo(C1-C6)alkoxy and (C 1 -C4)alkylthio and, in the case of cyclic radicals, also (Cl-C 4 )alkyl and (Cl-C 4 )haloalkyl, R 1is hydrogen, R 32is halogen, halo(CI -C 4 )alkyl, halo(Ci -C 4 )alkoxy, (Ci -C4)alkyl, (Ci -C 4 )alkoxy, (Ci -C 4 )alkylsulfonyl, (C 1

-C

4 )alkoxycarbonyl or (Ci -C 4 )alkylcarbonyl, preferably halogen, (01-C4)haloalkyl, such as trifluoromethyl, (Ci -C 4 )alkoxy, halo(Ci -C 4 )alkoxy, (Ci -C 4 )alkoxycarbonyl or (Ci -C 4 )alkylsulfonyl, R 3is hydrogen, R 34 is halogen, (Ci -C4)alkyl, halo(Cl-C4)alkyl, halo(Cl-C4)alkoxy,

(C

3 -C6)cycloalkyl, phenyl, (Ci -C 4 )alkoxy, cyano, (Ci -C4)alkylthio, (Ci -C 4 )alkylsulfinyl, (C 1

-C

4 )alkylsulfonyl, (Ci -C 4 )alkoxycarbonyl or (Ci -C 4 )alkylcarbonyl, preferably halogen, (Cl-C4)alkyl, (Cl-C4)haloalkyl, such as trifluoromethyl, halo(C 1

-C

4 )alkoxy, (Cl-C4)alkoxy or (Cl-C 4 alkylthio, n isO0, 1 or 2and mn isl1or 2.

Furthermore preferred are safeners of the formula in which X3 is OH; R 5is hydrogen, (Ci -C6)alkyl, (C3-C6)cycloalkyl, (02-C6)alkenyl, (C5-C6)cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl having up to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, it being possible for the six lastmentioned radicals to be optionally substituted by one or more identical or different substituents selected from the group consisting of halogen, (Cl-C6)alkoxy, (Cl-C6)haloalkoxy, (Cl-C2)alkylsulfinyl, (Ci -C2)alkylsu Ifonyl, (C3-C6)cycloal kyl, (Ci -C4)alkoxycarbonyl, (Cl-C4)alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (Ci -C4)alkyl and (Cl-C 4 )haloalkyl; R 36is hydrogen, (Cl-06)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, it being possible for the three last-mentioned radicals optionally to be substituted by one or more, identical or different substituents selected from the group consisting of halogen, hydroxyl, (Cl-C4)alkyl, (Cl-C4)alkoxy and (Cl-C4)alkylthio; R 7is halogen, (Ci -C4)haloalkyl, (Cl-C 4 )haloalkoxy, nitro, (Cl-C4)alkyl, (Ci -C4)alkoxy, (Cl-C4)alkylsulfonyl, (Ci -C4)alkoxycarbonyl or (Ci -C4)alkylcarbonyl; R 38 is hydrogen; R 9is halogen, nitro, (Ci -C4)alkyl, (Ci -C 4 )haloalkyl, (Cl-C4)haloalkoxy, (C3-C6)cycloalkyl, phenyl, (Cl-C4)alkoxy, cyano, (Ci -C4)alkylthio, (Ci -C4)al kylsulfinyl, (Ci -C4)alkylsulfonyl, (Ci -C4)alkoxycarbonyl or (Ci -C4)alkylcarbonyl; n isO0, 1 or 2and m isl1or 2.

Especially preferred amongst the safeners of the formula (VII) are the subgroups which follow: compounds in which R 4 8 and R 4 9 are H, (Cl-Cs)alkyl, phenyl, phenyl(C1-C8)alkyl, (C 1

-C

4 )alkoxy-(C1-C 8 )alkyl, (C3-C 6 )alkenyl or (C3-C6)alkynyl, it being possible for phenyl rings to be substituted by F, CI, Br, NO 2 CN, OCH 3 (C1-C4)alkyl or CH 3 -S02-; compounds in which R a is H; compounds in which R is Rb; compounds in which A is R; compounds in which E is CR2 1 47 compounds in which 4 7 is CR2; compounds in which R is H; compounds in which m" is 1 and E is O or S; compounds in which m" 0; compounds in which R 4 0 to R 4 4 are H, m" is 1, E is O, Q is CR 2 4 and A is Rb-Y, in particular those where R 4 7 is H, R b is CH3 and Y is 0; compounds in which Q1 is CR 2 47 and m" equals 0, in particular those in which R 4 4 and R 4 7 are H and A is Rb-Y 3 where R b is preferably methyl and Y is preferably O.

Examples of preferred combinations of herbicidal active substances (A) and safeners are: (111-1), (IV-1), (111-1), and The safeners (antidotes) of the formulae (II) (VII) and the compounds of group for example safeners of the preferred groups a) to reduce or prevent phytotoxic effects which may occur when using the herbicidal active substances of the formula in crops of useful plants without substantially affecting the efficacy of these herbicidal active substances against harmful plants. This allows the field of application of conventional crop protection products to be widened quite considerably and to be extended to, for example, crops such as wheat, barley, maize, rice and other crops in which use of the herbicides was hitherto impossible, or only limited, that is to say at low rates and with a restricted spectrum.

The herbicidal active substances and the mentioned safeners can be applied together (as a readymix or by the tank mix method) or in succession in any desired sequence. The weight ratio of safener:herbicidal active substance may vary within wide limits and lies preferably in the range of from 1:100 to 100:1, in particular 1:10 to 10:1. The optimum amounts of herbicidal active substance and safener which are used in each case depend on the type of the herbicidal active substance used or on the safener used and on the species of the crop stand to be treated and can be determined in each individual case by simple routine preliminary experiments.

The main fields of application for the combinations according to the invention are, in particular, maize and cereal crops (for example, wheat, rye, barley, oats), rice, sorghum, cotton and soybeans, preferably cereals, rice and maize.

Depending on their properties, the safeners contained in the herbicidal composition according to the invention can be used for pretreating the seed of a crop plant (seed dressing), or be incorporated into the seed furrows prior to sowing or applied together with the herbicide before or after plant emergence. The pre-emergence treatment includes not only treatment of the area under cultivation prior to sowing and treatment of the areas under cultivation where the seeds have been planted but the plants have not yet emerged. The joint application together with the herbicide is preferred. To this end, tank mixes or readymixes may be employed.

The application rates of safener required may vary within wide limits depending on indication and herbicidal active substance used and are generally in the range of from 0.001 to 5 kg, preferably 0.005 to 0.5 kg, of active substance per hectare.

The present invention furthermore relates to a method of controlling harmful plants in plant crops, which comprises applying a herbicidally effective amount of a herbicidally effective composition according to the invention to the harmful plants, crop plants, plant seeds or the area on which the plants grow. In this context, the antidote-effective amount of one or more safeners, preferably of one or more, in particular one, compound of the formula (111), (VII) and/or from among group can be applied to the plants, plant seeds or the area on which the plants grow before, after or simultaneously with the herbicidally active substance(s) of the formula The herbicide/safener combination according to the invention may also be employed for controlling harmful plants in crops of genetically engineered plants which are either known or still to be developed. As a rule, the transgenic plants are distinguished by particular, advantageous properties, for example by resistance to certain crop protection agents, resistance to plant diseases or pathogens causing plant diseases such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material in terms of quantity, quality, storing properties, composition and specific constituents. Thus, there are known transgenic plants with an increased starch content or with an altered starch quality, or those where the harvested material has a different fatty acid composition.

The use of the combinations according to the invention in economically important transgenic crops of useful plants and ornamentals, for example cereals (for example wheat, barley, rye, oats), sorghum and millet, rice, cassava and maize, or else crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other vegetables.

When the combinations according to the invention are applied in transgenic crops, effects on harmful plants to be observed in other crops are frequently accompanied by effects which are specific for application in the transgenic crop in question, for example an altered or specifically widened weed spectrum which can be controlled, altered application rates which may be used, preferably good compatibility with the herbicides to which the transgenic crop is resistant, and altered growth and yield of the transgenic crop plants.

The invention therefore also relates to the use of the herbicidally active composition according to the invention for controlling harmful plants in transgenic crop plants or crop plants that have tolerance owing to selection-based breeding.

The safeners, preferably of the formulae (11) (VII) and/or of group B(b), and the abovementioned herbicidal active substances of the formula can be formulated in various ways, either jointly or separately, depending on the biological and/or chemico-physical parameters specified. Examples of possible formulations which are suitable are: Wettable powders emulsifiable concentrates water-soluble powders water-soluble concentrates concentrated emulsions (BW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions oil- or water-based dispersions suspoemulsions, suspension concentrates, dusts oil-miscible solutions seed-treatment products, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, granules for soil application or broadcasting, water-soluble granules (SG), water-dispersible granules ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and described, for example, in: Winnacker-KOchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4 t h Edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker 1973; K.

Martens, "Spray Drying Handbook", 3rd Edition 1979, G. Goodwin Ltd.

London.

The formulation auxiliaries which may be required, such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley Sons, C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ.

Co. Inc., N.Y. 1964; Schinfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-Active Ethylene Oxide Adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-KOchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4 th Edition 1986.

Based on these formulations, it is also possible to prepare combinations with other agrochemical active substances, for example with substances which act as crop protection agents, such as insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a readymix or tank mix.

Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also comprise ionic and/or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate, or else sodium oleoylmethyltaurinate, in addition to a diluent or inert substance. To prepare the wettable powders, the active substances, for example the herbicidally active substances and/or the safeners are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.

Emulsifiable concentrates are prepared, for example, by dissolving the active substance, for example the herbicidal active substance and/or the safener, in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling hydrocarbons such as aromatics, saturated or unsaturated aliphatic hydrocarbons or alicyclic hydrocarbons, or mixtures of the organic solvents with the addition of one or more ionic and/or nonionic surfactants (emulsifiers). Examples of substances which can be used as emulsifiers are: calcium (C6-C18)alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, (C2-C18)alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

Dusts are generally obtained by grinding the active substance, for example the herbicidal active substance and/or the safener, with finely distributed solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet grinding using commercially available bead mills with or without an addition of surfactants, for example those which have already been mentioned above in the case of the other formulation types.

Emulsions, for example oil-in-water emulsions can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents in the presence or absence of surfactants which have already been mentioned above, for example, in the case of the other formulation types.

Granules can be prepared either by spraying the active substance, for example the herbicidal active substance and/or the safener, onto adsorptive, granulated inert material or by applying active substance concentrates to the surface of carriers such as sand, kaolinites or granulated inert material with the aid of binders, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active substances can also be granulated in the manner which is conventional for the preparation of fertilizer granules, if desired as a mixture with fertilizers.

As a rule, water-dispersible granules are prepared by the customary processes such as spray drying, fluidized bed granulation, disk granulation, mixing with high-speed mixers, and extrusion without solid inert material.

For the preparation of disk, fluidized-bed, extruder and spray granules see, for example, processes in "Spray-Drying Handbook" 3 rd Ed. 1979, G.

Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 et seq.; "Perry's Chemical Engineer's Handbook", 5 th Ed., McGraw-Hill, New York 1973, p. 8-57.

For further details on the formulation of crop protection products see, for example, G.C. Klingman, 'Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5 th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

As a rule, the agrochemical formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active substances, for example safener active substances preferably of the formula (11) (VII) and/or from among group or herbicidal active substances of the formula or of the herbicide/safener active substance mixture according to the invention, comprising compounds of the formula and safener active substances preferably compounds of the formula (II) (VII) and/or from among group and 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid additive and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.

In wettable powders, the active substance concentration is, for example, approximately 10 to 90% by weight, the remainder to 100% by weight being composed of customary formulation components. In the case of emulsifiable concentrates, the concentration of active substance is approximately 1 to 80% by weight. Formulations in the form of dusts comprise 1 to 20% by weight of active substance, sprayable solutions comprise approximately 0.2 to 20% by weight of active substance. In the case of granules, such as water-dispersible granules, the active substance content depends partly on whether the active compound is in liquid or solid form. The active substance content of the water-dispersible granules is, for example, between 10 and 90% by weight.

Besides this the abovementioned formulations of active substances may comprise, if appropriate, the adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and pH and viscosity regulators which are customary in each case.

Components which can be used in combination with the mixtures according to the invention in mixed formulations or in tank mixes are, for example, known active substances as they are described, for example, in Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 10 th edition, The British Crop Protection Council, 1994, and the literature cited therein.

Examples of active substances which may be mentioned as herbicides which are known from the literature and which can be combined with the mixtures according to the invention are the following (note: either the common names in accordance with the International Organization for Standardization (ISO) or the chemical names, if appropriate together with a customary code number, of the compounds are given): acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4- (trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetic acid and its methyl ester; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, iLe. ammonium sulfamate; anilofos; asulam; atrazine; azafenidine (DPX-R6447), azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3, 1-benzoxazin-4one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac-sodiumn (KIH-2023), bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachior; butamifos; butenachior; buthidazole; butralin; butroxydim (101-0500), butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, i.e.

2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chioroallyl diethyldithiocarbamate; chiomethoxyfen; chioramben; chioransulamn-methyl (XIDE-565), chiorazifop-butyl, chlorbromuron; chlorbufam; chiorfenac; chiorfiurecolmethyl; chioridazon; chiorimuron ethyl; chiornitrofen; chiorotoluron; chioroxuron; chiorpropham; chiorsulfuron; chiorthal-dimethyl; chiorthiamid; cinidon-ethyl, cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives clod inafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumnyluron (JO 940); cyanazine; cycloate; cyclosulfamuron (AC 014); cycloxydim; cycluron; cyhalofop and its ester derivatives butyl ester, DEH-1 12); cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichiobenil; dichiorprop; diclofop and its esters such as diclofop-methyl; diclosulamn (XIDE-564), diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyrsodium (SAN-835H), dimefuron; dimethachior; dimethametryn; dimethenamid (SAN-582H); dimethazone, 5-(4,6-dimethylpyrimidin-2-yIcarbamoylsulfamoyl)-1 -(2-pyridyl)-pyrazole-4-carboxylate (NC-330); triaziflam (IDH-1 105); clomazon; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, i.e. 5-cyano-1-(1,1-dimethylethyl)-Nmethyl-i H-pyrazole-4-carboxamide; endothal; epoprodan (MK-243), EPTC; esprocarb; ethalfiuralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluorpropyl)-4,5d ihyd ro-5-oxo-1 H-tetrazol- 1 -yl]phenyl]ethanesulfonamide; ethoxyfen and its esters ethyl ester, HN-252); ethoxysulfuron (disclosed in EP 342569) etobenzanid (HW 52); 3-(4-ethoxy-6-ethyl-1 ,3,5-triazin-2-yl -(2,3-dihydro- 1 ,1-dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea (EP-A 079 683); 3-(4ethyl-6-methoxy-1 5-triazin-2-yl)-l1-(2 ,3-dihydro-1 ,1 -d ioxo-2methylbenzo[b]thiophene-7-sulfonyl)urea (EP-A 079 683); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and their esters, e.g. fenoxaprop-Pethyl and fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl; flazasulfuron; flufenacet (BAY-FOE-5043), fluazifop and fluazifop-P, florasulam (DE-570) and their esters, e.g. fluazifop-butyl and fluazifop-Pbutyl; fluchioralin; flumetsulam; flumeturon; flumiclorac and their esters pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); flupyrsulfuron-methyl sodium (DPX-KE459), fluridone; flurochioridone; fluroxypyr; flurtamone; fluthiacet-methyl (KIH-9201), fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron and its esters methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P Rhaloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazamox (AC-299263), imazapyr; imazaquin and salts such as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron; iodosulfuron (methyl-4iod o-2- ethoxy-6-m ethyl-1, ,3,5-tri azi n-2-yl )ure id osulIfonyl]-be nzoate, sodium salt, WO 92/13845); loxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MOPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobenzuron, methyl-2-[3-(4,6-dimethoxypyrimidin-2yl )u reidosulfonyl]-4-methanesulfonamidomethylbenzoate (WO 95/10507); methobenzuron; metobromuron; metolachlor; S-metolachlor, metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2methylpentanamide; N, N-d imethyl-2-[3-(4,6-d imethoxypyrimid in-2yl)ureidosulfonyl]-4-formylaminobenzamide (WO 95/01344); naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1 benzyloxypyrazole; neburon; nicosulfuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen; norfiurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxaziclomefone (MY- 100), oxyfluorfen; oxasulfuron (CGA- 277476), paraquat; pebulate; pendimethalin; pentoxazone (KPP-314), perflidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochior; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA- 152005); prynachlor; pyraflufen-ethyl (ET-75 pyrazon; pyrazosulfuronethyl; pyrazoxyfen; pyribenzoxim, pyridate; pyriminobac-methyl (KIH-6127), pyrithiobac (KIH-2031); pyroxofop and its esters propargyl ester); quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and quizalofop-P and their ester derivatives e.g. quizalofop-ethyl; quizalofop-Ptefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e. 2- [4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2- [[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]-propanoic acid and its methyl ester; sulfentrazon (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebuthiuron; tepraloxydim (BAS-620H), terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e.

N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1 H-1,2,4-triazole-1 carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-124085); thifensulfuron-methyl; thiobencarb; thiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and esters (e.g.

methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, i.e.

5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; KPP-421, MT-146, NC-324; KH-218; DPX-N8189; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001.

For use, the formulations which are in commercially available form are, if desired, diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, soil granules, granules for broadcasting and sprayable solutions are usually not diluted any further with other inert substances prior to use.

The necessary application rate of the herbicides of the formula varies with the external conditions such as, inter alia, temperature, humidity and the nature of the herbicide used. It may be varied within wide limits, for example between 0.001 and 10.0 kg/ha or more of herbicide, but it is preferably between 0.005 and 5 kg/ha.

The examples which follow are intended to illustrate the invention: A. Formulation Examples a) A dust is obtained by mixing 10 parts by weight of a herbicidal active ingredient of the formula or of a compound of the formula (II) (VII) and/or from amongst group or of an active substance mixture of a herbicidal active substance of the formula and a safener of the formula (II) (VII) and/or from amongst group B(b) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a herbicidal active ingredient of the formula or of a compound of the formula (II) (VII) and/or from the group B(b) or of an active substance mixture of a herbicidal active substance of the formula and a safener of the formula (II) (VII) and/or from amongst group 64 parts by weight of kaolincontaining quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetter and dispersant and grinding the mixture in a pinned-disk mill.

c) A concentrate which is readily dispersible or suspendible in water is obtained by mixing 20 parts by weight of a herbicidal active ingredient of the formula or of a compound of the formula (II) (VII) and/or from amongst group B(b) or of an active substance mixture of a herbicidal active substance of the formula and a safener of the formula (II) (VII) and/or from amongst group B(b), 6 parts by weight of alkylphenol polyglycol ether (@Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, approx. 255 to above 277 0 C) and grinding the mixture in a ball mil to a fineness of below 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a herbicidal active ingredient of formula or of a compound of the formula (II) (VII) and/or from amongst group B(b) or of an active substance mixture of a herbicidal active substance of the formula (I) and a safener of the formula (II) (VII) and/or from amongst group 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

e) Water-dispersible granules are obtained by mixing parts by weight of a herbicidal active ingredient of formula or of a compound of the formula (II) (VII) and/or from amongst the group B(b) or of an active substance mixture of a herbicidal active substance of the formula and a safener of the formula (II) (VII) and/or from amongst group B(b), of calcium lignosulfonate 5 of sodium lauryl sulfate, 3 of polyvinyl alcohol and 7 of kaolin, grinding the mixture on a pinned-disk mill and granulating the powder in a fluidized bed by spraying on water as the granulation liquid.

f) Water-dispersible granules are also obtained by homogenizing and precomminuting, on a colloid mill, part(s) by weight of a herbicidal active ingredient of formula or of a compound of the formula (II) (VII) and/or from amongst group B(b) or of an active substance mixture of a herbicidal active substance of the formula and a safener of the formula (II) (VII) and/or from amongst group B(b) of sodium 2,2'-dinaphthylmethane-6,6'disulfonate 2 of sodium oleoylmethyltaurinate, 1 of polyvinyl alcohol, 17 of calcium carbonate and of water, subsequently grinding the mixture on a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a single-substance nozzle.

Biological Examples 1. Scoring the damage The damage to the plants is assessed visually in comparison with control plants on a scale of 0-100%: 0% no noticeable effect in comparison with the untreated plant, 100% treated plant dies.

2. Post-emergence herbicide action Seeds of monocotyledonous and dicotyledonous weed plants and of crop plants are placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions.

Three weeks after sowing, the test plants are treated in the 3-4 leaf stage.

The individual active substances according to the invention which are formulated as emulsion concentrates are sprayed onto the green parts of the plants individually or as mixtures in various dosages at a water application rate of 300 I/ha (converted) and, after the test plants have been left in the greenhouse for 3 weeks under ideal growth conditions, the effect of the products was scored visually by comparison with untreated controls.

The results are given in Table 1, which follows.

Table 1: Active substances (I-1) (I-1) (I-1) Dose g a.s./ha 100 50 25 100+100 50+50 25+25 100+100 50+50 25+25 (1-1) (1-1) (I-1) (11-1) (11-1) (11-1) (111-1) (111-1) (111-1) Damage Wheat 0 0 Barley (11-9) 50+50 Abbreviations: g a.s./ha g of active substance per hectare The terms (111-1) and (11-9) are explained in the description.

As shown in the examples, the combinations according to the invention of herbicides and safeners are capable of substantially reducing damage to crop plants such as cereals as compared with the use of the individual herbicides without safener.

Claims (4)

1. 06-Clo-haloaryl, Ci -C 6 -alkylsulfonyl-Ci -C4-alkyl, di(Cl-C 6 alkyl)phosphono-Ci -04-alkyl, tri(Ci -C6-alkyl)silyl-CI -C4alkyl), C2-C7-alkanoyl-Cli-C 4 -alkyl, carboxy-C 1-04-a Ikyl, (01 -06- alI koxy)ca rbo nyl-C 1 -4aIkyl, {[C3-C9(ct-alkylalkylidene)]iminooxy- (C 1 -C6-alIkoxy)ca rbo nyl}-C 1 -0 4 -alIkyl, (C3-C6-alkenyloxy)carbonyl- Ci -04-alkyl, (03-06-alI kyn yloxy)ca rbo nyl-C I -04-alIkyl, (03-08- cycloal kyloxy)carbonyl-Cli-C 4 -alkyl, phenoxy-Cl1-04-alkyl, .03-06- alkenyloxy-Cli-04-alkyl, C3-C8-cycloalkenyloxy-C1 -04-al kyl, 05-08- cycloal kenyl, C6-C8-bicycloalkyl, 06-08-bicycloalkenyl, 02-07- cyanoalkyl or C3-C6-alkynyloxy-C1 -04-a Ikyl, R 3 is hydrogen, halogen or cya no, R4 is hydrogen or halogen, is hydrogen, halogen or 01-04-alkyl, and R 6 is 01-04-alkyl or Cl-C 4 -haloalkyl, or R 5and R 6together form trimethylene or tetramethylene, and the 1corresponding enol ethers of the compound of the formula in which Ris other than hydrogen and Ci-04-haloalkyl, and the salts of the compound of the formula in which R1is hydrogen, 41 and an antidote-effective amount of one or more safeners, wherein the safeners(s) is/are selected from the group consisting of compounds of the formulae (II) or (III), O (R1 9 )n (R 17 0 W R 18 O CO OT (II) (111) where the symbols and indices having the following meanings: n' is a natural number form 0 to 5, preferably 0 to 3; 10 T is a (Ci or C 2 )-alkanediyl chain which is unsubstituted or substituted by one or two (C 1 -C4)alkyl radicals or by [(C 1 -C 3 )-alkoxy]carbonyl; W is an unsubstituted or substituted divalent heterocyclic radical selected from the group consisting of the partially unsaturated or aromatic five- ringed heterocycles having 1 to 3 hetero ring atoms of the type N or O, the 15 ring containing at least one nitrogen atom and not more than one oxygen atom, preferably a radical selected from the group consisting of (W1) to (W4), **b*o N -(CH2)m' N N N r R 29 O-N R 27 COOR 26 R 27 R 28 (W1) (W2) (W3) (W4) m' is 0 or 1; R 17 R 19 are identical or different halogen, (Ci-C 4 )alkyl, (Ci-C4)alkoxy, nitro or (C 1 -C4)haloalkyl; 42 R 18 R 20 are identical 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 nitrogen atom and up to 3 hetero atoms, preferably from the group consisting of O and S, which heterocycle is linked to the carbonyl group in (II) or (III) via the nitrogen atom and which is unsubstituted or substituted by radials selected from the group consisting of (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy or optionally substituted phenyl, preferably a radical of the formula OR 24 NHR 25 or N(CH 3 2 in particular of the formula OR 24 R 24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms; R 25 is hydrogen, (C1-C 6 )alkyl, (C 1 -C 6 )alkoxy or substituted or unsubstituted phenyl; R 26 is hydrogen, (C 1 -C 8 )alkyl, (C 1 -Cs)haolalkyl, (C1-C4)alkoxy-(C 1 -C 4 )alkyl, (C1- C 6 )hydroxyalkyl, (C 3 -C 12 )cycloalkyl or tri-(C 1 -C4)-alkylsilyl; S 15 R 27 R 28 R 29 are identical or different hydrogen, (C 1 -Cs)alkyl, (C 1 -C 8 )haloalkyl, (C 3 -C 12 )cycloalkyl or substituted or unsubstituted phenyl; inclusive of the stereoisomers and of the salts conventionally used in agriculture. 2. A herbicidally active composition as claimed in claim 1, where, in a compound of the formula (I) R 1 is C 1 -C 4 -alkyl, preferably methyl, R 2 is C 2 -C 7 -alkanoyl-C 1 -C 4 -alkyl, (C 1 -C 6 -alkoxy)carbonyl-C1-C 4 -alkyl, C1-C4- alkyl, {[C 3 -C9-(a-alkylalkylidene)iminooxy-(C1-C 6 -alkoxy)carbonyl]-C1-C 4 -alkyl, (C3-C 6 -alkenyloxy)carbonyl-C 1 -C 4 -alkyl, (C 3 -C 6 -alkynyloxy)carbonyl-C 1 -C 4 -alkyl or (C 3 -C 8 -cycloalkyloxy)carbonyl-C 1 -C 4 -alkyl, R 3 is halogen or cyano, R 4 is hydrogen or fluorine, R 5 is hydrogen, fluorine or methyl, and R 6 is methyl, trifluoromethyl or pentafluoroethyl. 3. A herbicidally active composition as claimed in one or more of claims 1 to 2, wherein the weight ratio herbicide:safeners is 1:100 to 100:1. 4. A herbicidally active composition as claimed in one or more of claims 1 to 3, additionally containing one or more further agrochemical active ingredients. A method of controlling harmful plants in plant crops, which comprises applying a herbicidally effective amount of a herbicidally active composition as claimed in one or more of claims 1 to 4 to the harmful plants, the crop plants, the seeds of the plants or the area on which the plants grow. 6. The method as claimed in claim 5, wherein the crop plants are selected from the group consisting of maize, wheat, rye, barley, oats, rice, sorghum, cotton and soya.
2. 7. The method as claimed in claim 5 or 6, wherein the crop plants are S transgenic or have tolerance owing to selection-based breeding. The use of a herbicidally active composition as claimed in one or more of claims 1 to 4 for controlling harmful plants in plant crops. o
3. 9. A herbicidally active composition according to any one of claims 1 to 4 15 substantially as hereinbefore described.
4. 10. A method of controlling harmful plants in plant crops according to any one of claims 5 to 7 substantially as hereinbefore described. DATED this 8th day of December 2004 AVENTIS CROPSCIENCE GMBH WATERMARK PATENT TRADE MARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA P20886AU00 BMHVRH