AU766323B2 - Herbicide/safener combination products - Google Patents

Abstract

The invention relates to a herbicidally active agent that contains a mixture from A) a herbicidally active amount of one or more compounds of the formula (I), wherein X and Y are the same or different and represent hydrogen, halogen, for example fluorine, chlorine, bromine or iodide, Z represents -S-CHR<1>-COOR<2>, wherein R<1> represents hydrogen or C1-C20 alkyl, preferably C1-C6 alkyl, R<2> represents C1-C20 alkyl, C3-C8 cycloalkyl or C1-C10-alkoxy-C1-C10-alkyl, preferably C1-C6 alkyl, C4-C6 cycloalkyl or C1-C4-alkoxy-C1-C4 alkyl, or -COOR<3>, wherein R<3> represents C1-C20 alkyl, preferably C1-C6 alkyl, or Y and Z together represent a group -O-CHR<4>-CO-NR<5>- that forms a ring with the phenyl ring, wherein R<4> represents hydrogen or C1-C20 alkyl, preferably C1-C6 alkyl, and R<5> represents C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkinyl, preferably C1-C6 alkyl, C3-C5 alkenyl or C3-C5 alkinyl; and B) an antidotically effective amount of one or more safeners.

Description

WO 01/08488 PCT/E P00/07054 Combinations of herbicides and safeners Description 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-273 417 discloses herbicidally active substances which control a broad spectrum of weeds and which, alone or as a mixture with other active substances, can be employed for [lacuna] important weeds, mention being made both of what is called the nonselective use together with nonselective foliar-acting herbicides and of 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 2 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 with regard to important crop plants is increased. Surprisingly, this object is achieved by the herbicidal compositions of the present invention.

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

(I)

N

I S Z 0 in which X and Y are identical or different and are hydrogen or halogen such as fluorine, chlorine, bromine or iodine, Z is -S-CHR -COOR 2 in which R is hydrogen or C1-C20-alkyl, preferably C1-C 6 -alkyl,

R

2 is C1-C 2 0 -alkyl, C3-C8-cycloalkyl or C 1 -Co1-alkoxy-C1-C o-alkyl, preferably C1-C6-alkyl, C4-C6-cycloalkyl or C1-C 4 -alkoxy- 3

C

1

-C

4 -alkyl, or is -COOR 3 where R 3 is C 1

-C

2 o-alkyl, preferably C1-C 6 -alkyl, or Y and Z together form a group -O-CHR 4

-CO-NR

5 which, together with the phenyl ring, forms a ring in which R 4 is hydrogen or C1-C20-alkyl, preferably C 1

-C

6 -alkyl, and R 5 is C 1

-C

20 -alkyl, C 2 -C20-alkenyl or

C

2 -C2 0 -alkynyl, preferably C 1 -C6-alkyl, C 3

-C

5 -alkenyl or and an antidote-effective amount of one or more safeners.

In formula Z is preferably -S-CH(CH 3

)-COOR

2 or where R 2 is C1-C 6 -alkyl or C 4 -C6-cycloalkyl.

The compound of the formula is preferably described formula (la)

-S-CH

2

-COOR

2 by the following x I S Z in which X is hydrogen or halogen, preferably fluorine, Y is halogen, preferably chlorine, and 2 Z is as defined in formula and is preferably -S-CH(CH 3 )-COOR or

-S-CH

2

-COOR

2 where R 2 is C 1

-C

6 -alkyl or C 4

-C

6 -cycloalkyl.

An especially preferred compound of the formula is fluthiacet-methyl Pesticide Manual, 11th Edition, British Crop Protection Council, pp 606-608, entry No. 359).

The safeners are preferably selected from the group consisting of a) compounds of the formulae (II) to (IV), 0

(R

1 7

I

R18

(II)

(R19)n, TZ C0-" R2 (111) j

R

2 3

(IV)

where n'

T

the symbols and indices having the following meanings: is a natural number from 0 to 5, preferably 0 to 3; is a (C1 or C 2 )-alkanediyl chain which is unsubstituted or substituted by one or two (C1-C 4 )alkyl radicals or by [(C1-C3)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 0, 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

R27

COOR

26 (W1)

R

27 (W2) 2 N N -(CH R 2 9 (W3) (W4) m' is 0 or 1; 17 19 R R 1 are identical or different halogen, (C1-C4)alkyl, (C1-C 4 )alkoxy, nitro or (C1-C 4 )haloalkyl; 18 20 24 24 24 25 R 8 R are identical or different OR 2

SR

2 4 or NR24R 2 5 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 0 and S, which is linked to the carbonyl group in (11) or (1ll) via the nitrogen atom and which is unsubstituted or substituted by radicals selected from the group consisting of (Cl-C 4 )alkyl, (Ci -C 4 )alkoxy or optionally 24 substituted phenyl, preferably a radical of the formula OR NHR 25or N(CH 3 2 in particular of the fomula OR 2 R 24is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having in total 1 to 18 carbon atoms; R 25is hydrogen, (Cl-C6)alkyI, (Cl-C 6 )alkoxy or substituted or 26 unsubstituted phenyl; R is hydrogen, (Ci -C8)alkyl, (Ci -C 8 )haloalkyl, (Ci -C4)alkoxy- (Ci -C4)alkyl, (Ci -06) hyd roxyal kyl, (03-Cl 2)cycloalkyl or tri- (Ci -04)-alkylsilyl; R 2, R 2, R 29are identical or different hydrogen, (Ci -C8)alkyl, (Ci -C8)haloalkyl, (03-Cl 2)cycloalkyl or substituted or 21 unsubstituted phenyl; R is (Ci -C4)alkyl, (Ci -C 4 )haloalkyl, (C2-C4)alkenyl, (02-04)haloalkenyl, (C3-C7)cycloalkyl, preferably dichloromethyl; R 2, R 23is identical or different hydrogen, (Cl-C4)alkyl, (C2-04)alkenyl, (C2-C4)alkynyl, (Ci -C 4 )haloalkyl, (C2-C4)haloalkenyl, (Ci -C4)alkylcarbamoyl-(Cl -04)alkyl, (02-04)alkenylcarbamoyl-(Cl -C4)alkyl, (Ci -C4)alkoxy-(0 1 -04)alkyl, dioxolanyl-(Ci -C 4 )alkyl, thiazolyl, furyl,. furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R 22and R 2 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; b) one or more compounds from the group consisting of: 1 ,8-naphthalic anhydride, methyl diphenylmethoxyacetate, cyanomethoxyimino(phenyl)acetonitrile (cyometrinil), 1 ,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil), 4'-ch lo ro-2,2,2-trifluo roacetop he none 0-1 ,3-dioxolan-2-ylmethyloxime (fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl-2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole), 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), N-(4-methylphenyl)-N'-(1 -methyl-1 -phenylethyl)urea (dymron), 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1 -[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea, 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, (2,4-dichlorophenoxy)acetic acid (4-chlorophenoxy)acetic acid, (R,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-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1 -(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor) and their salts and esters, preferably (C1-C8); c) N-acylsulfonamides of the formula and their salts,

R

31

R

3 3 (R34\ 0R30 S N (V) 0

(R

32 where

R

30 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbonthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, each of the last-mentioned 4 radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, carboxamide, sulfonamide and radicals of the formula -Za-R a each hydrocarbon moiety preferably having 1 to 20 carbon atoms and a carbon-containing radical R inclusive of substituents preferably having 1 to 30 carbon atoms; R is hydrogen or (Ci-C4)alkyl, preferably hydrogen, or

R

30 and R 31 together with the group of the formula -CO-N- are the radical of a 3- to 8-membered saturated or unsaturated ring; 32 R is identical or different halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH 2

SO

2

NH

2 or a radical of the formula -ZbRb;

R

33 is hydrogen or (C1-C4)alkyl, preferably H;

R

34 is identical or different halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH 2

SO

2

NH

2 or a radical of the formula -Z-RC;

R

a is a hydrocarbon radical or a heterocyclyl radical, each of the two last-mentioned radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [(C1-C4)alkyl]amino, or is an alkyl radical in which more than one, preferably 2 or 3, nonadjacent CH 2 groups are each replaced by an oxygen atom; Rb,R c identical or different are a hydrocarbon radical or a heterocyclyl radical, each of the two last-mentioned radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halo(C 1 -C4)alkoxy, mono- and di[(C 1 -C4)alkyl]amino, or are an alkyl radical in which more than one, preferably 2 or 3, nonadjacent CH 2 groups are each replaced by an oxygen atom;

Z

a is a divalent group of the formula -CO-O-, -S02-, -NR*-CO-, -SO2-NR*- or -NR*-SO2-, the bond shown on the right of the divalent group in question being the bond to the radical R a and the R* in the last-mentioned 5 radicals independently of one another being in each case H, (C1-C4)alkyl or halo(C1-C4)alkyl; b c Zb,Z independently of one another are a direct bond or a divalent group of the formula -S-CO-,

-SO

2 -SO2-NR*-, -NR*-SO2-, -CO-NR*- or -NR*-CO-, the bond shown on the right of the divalent group in question being the bond to the radical R b or R c respectively, and the R* in the lastmentioned 5 radicals independently of one another being in each case H, (C1-C4)alkyl or halo(C 1

-C

4 )alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular 0 or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; d) acylsulfamoylbenzamides of the formula if appropriate in salt form,

O

R

35 R36 v I v l o

(R

37 )n R8 where

X

3 is CH or N;

R

35 is hydrogen, heterocyclyl or a hydrocarbon radical, the two lastmentioned radicals optionally being substituted by one or more, identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH 2

SO

2

NH

2 and Za-Ra

R

3 6 is hydrogen, hydroxyl, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl,

(C

1

-C

6 )alkoxy, (C2-C6)alkenyloxy, the five last-mentioned radicals optionally being substituted by one or more identical or different radicals selected from the group consisting of halogen, hydroxyl, (Cl-C4)alkyl, (C1-C4)alkoxy and (Ci-C4)alkylthio, or

R

3 5 and R 3 6 together with the nitrogen atom to which they are attached are a 3- to 8-membered saturated or unsaturated ring;

R

7 is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH 2

SO

2

NH

2 or Zb-Rb

R

3 8 is hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl or (C2-C4)alkynyl;

R

3 9 is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO, CONH 2

SO

2

NH

2 or ZC-R;

R

a is a (C2-C20)alkyl radical whose carbon chain is interrupted once or more by oxygen atoms, or is heterocyclyl or a hydrocarbon radical, the two last-mentioned radicals optionally being substituted by one or more, identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di[(C1i-C4)alkyl]amino;

R

b

R

c identical or different are a (C2-C 2 o)alkyl radical whose carbon chain is interrupted once or more by oxygen atoms, or are heterocyclyl or a hydrocarbon radical, the two last-mentioned radicals optionally being substituted by one or more, identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, (C1-C 4 )haloalkoxy, mono- and di[(C1-C 4 alkyl]amino;

Z

a is a divalent unit selected from the group consisting of O, S, CO, CS, C(0)O, C(0)S, SO, S02, NR d C(0)NR d or S0 2 NRd b c

Z

b Z identical or different are a direct bond or a divalent unit selected from the group consisting of O, S, CO, CS, C(0)O, C(0)S, SO, S02,

NR

d S0 2

NR

d or C(O)NRd

R

d is hydrogen, (C1-C4)alkyl or (C1-C4)haloalkyl; n is an integer from 0 to 4, and m in the event that X is CH, is an integer from 0 to 5 and, in -the event that X is N, an integer from 0 to 4; e) compounds of the formula (VII), R4 0 Qi R41 Q2IE)

(VII)

R42 where the symbols and indices have the following meanings:

R

4 0 is H, (C1-C 4 )alkyl, (C1-C4)alkyl substituted by (C1-C4)alkyl-X 4 or 4 43 44 (C1-C 4 )haloalkyl-X (C1-C 4 )haloalkyl, NO 2 CN, -COO-R 4 3 NR244 S02NR245 or CONR246

R

4 1 is H, halogen, (C1-C 4 )alkyl, CF 3 (C1-C 4 )alkoxy or (C1-C4)haloalkoxy;

R

4 2 is H, halogen or (C1-C4)alkyl; 1 2 47 48 Q Q E, G are identical or different, -CR247-, NR 4 or a group of the formula (VIII),

C=CH-O-CR

2 a-(CO)-A (VIII) with the proviso that 1 2 a) at least one of the groups Q Q E, G is a carbonyl group, that exactly one of this group is a radical of the formula (VIII) and that the group of the formula (VIII) is adjacent to a carbonyl group, and 1 2 3) two adjacent groups Q 0 Q2, E and G cannot simultaneously be oxygen; Ra is identical or different H or (C1-C 8 )alkyl or the two radicals Ra together are (C2-C6)alkylene; A is Rb -Y3_ or -NR 2 49 4 is o X 3 is or b Y is or Rb is H, (C1-C8)alkyl, (C1-C8)haloalkyl, (C1-C 4 )alkoxy(C1 -C8)alkyl, (C3-06)alkenyloxy(C -C 8 )alkyl, or phenyl(C1-C 8 )alkyl, the phenyl ring optionally being substituted by halogen, (C1-C 4 )alkyl, CF 3 methoxy or methyl-S(O)p; (C 3 -0 6 )alkenyl, (C3-C6)haloalkenyl, phenyl(C3-C6)alkenyl, (C 3 -C6)alkynyl, phenyl(C3-C6)alkynyl, oxetanyl, furfuryl, tetrahydrofuryl; R is H or (C1-C 4 )alkyl; R44 is identical or different H, (C-C 4 )alkyl, (C1-C 4 )alkylcarbonyl or the two radicals R44 together are 46 R6 are independently of one another in each case identical or different H, (C1-C 4 )alkyl, or the two radicals R45 and/or R46 together are (C 4 -0 5 )alkylene, it being possible for one CH 2 group to be replaced by O or S or by one or two CH 2 groups to be replaced by c

-NR-;

RC is H or (C1 -C)alkyl; R 47 is identical or different H, (C1-Cs)alkyl or the two radicals R47 together are (C2-C6)alkylene; R48 is H, (C1-C8)alkyl, substituted or unsubstituted phenyl, or benzyl which is unsubstituted or substituted on the phenyl ring; R49 is identical or different H, (C1-C)alkyl, phenyl, phenyl(C1-C)alkyl, it being possible for a phenyl ring to be substituted by F, CI, Br, NO 2 CN, OCH 3 (C1-04)alkyl or CH 3

SO

2 or is (C1-C 4 )alkoxy- (C1-C 8 )alkyl, (C3-C 6 )alkenyl, (C3-O6)alkynyl, (C 3 -C6)cycloalkyl or two radicals R49 together are (C 4 -0 5 )alkylene, it being possible for one CH2 group to be replaced by 0 or S or for one or two CH2 groups to be replaced by -NRd Rd is H or (C1-C4)alkyl; m" is 0 or 1 and p is 0, 1 or 2; inclusive of the stereoisomers and of the salts conventionally used in agriculture.

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.

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-1-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-1-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

CH

2 F, CF3CF 2

CH

2 FCHCI, CC13, CHCI 2

CH

2

CH

2 CI. Haloalkoxy is, for example, OCF 3 12

OCHF

2

OCH

2 F, CF 3

CF

2 0, OCH 2

CF

3 and OCH 2

CH

2 CI. 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 being, generally, 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, 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 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, the 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 heteraryl, for example 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, the 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-C4)haloalkyl, preferably trifluoromethyl,

(C

1

-C

4 )alkoxy, preferably methoxy or ethoxy, (C 1

-C

4 )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 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 CI 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, (C1-C4)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-C 4 -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-273 417, which contains detailed information on preparation methods, starting materials and preferred compounds. This publication is expressly referred to; it is incorporated into the present description 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 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 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: R is hydrogen, (C1-C18)alkyl, (C3-C12)cycloalkyl, (C2-C8)alkenyl and

(C

2 -C1 8 )alkynyl, it being possible for the carbon-containing groups to be substituted by one or more, preferably up to three, radicals

R

5 0 is identical or different halogen, hydroxyl, (C1-C 8 )alkoxy, (C1-C 8 )alkylthio, (C 2

-C

8 )alkenylthio, (C2-C8)alkynylthio, (C 2

-C

8 alkenyloxy, (C 2

-C

8 )alkynyloxy, (C3-C7)cycloalkyl, (C 3 -C7)cycloalkoxy, cyano, mono- and di(C 1 -C4)alkyl)amino, carboxyl,

(C

1 -C8)alkoxycarbonyl, (C2-C8)alkenyloxycarbonyl, (C 1 -C8)alkylthiocarbonyl, (C 2

-C

8 )alkynyloxycarbonyl, (C 1 -C8)alkylcarbonyl, (C2-C8)alkenylcarbonyl, (C 2

-C

8 )alkynylcarbonyl, 1 -(hydroxyimino)- (Ci -C 6 )alkyl, 1 1

-C

4 )alkylimino](Ci -C4)alkyl, 1 -C4)alkoxyimino](Ci -C6)alkyl, (Ci -C 8 )alkylcarbonylamino, (C2-C8)alkenylcarbonylamino, (C 2

-C

8 )alkynylcarbonylamino, aminocarbonyl, (Ci -C8)alkylaminocarbonyl, di(Ci -C6)alkylaminocarbonyl, (C 2

-C

6 alkenylaminocarbonyl, (C 2

-C

6 )alkynylaminocarbonyl, (Ci -C8)alkoxycarbonylamino, (Ci -C 8 )alkylaminocarbonylamino, (Ci -C 6 )alkylcarbonyloxy, which is unsubstituted or substituted byR (C2-C 6 )alkenylcarbonyloxy, (C 2

-C

6 )alkynylcarbonyloxy, (Ci -08)alkylsulfonyl, phenyl, phenyl(Ci -C 6 )alkoxy, phenyl(Ci -C 6 )alkoxycarbonyl, phenoxy, phenoxy(Ci -C 6 )alkoxy, phenoxy(Ci -C6)alkoxycarbonyl, phenylcarbonyloxy, phenylcarbonylamino, phenyl(C 1

-C

6 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 R 52; SiR' 3 -0-SiR' 3

R'

3 Si-(Ci -C 8 )alkoxy, -CO-0-NR' 2 -0-N=CR' 2

-N=C!R'

2 -0-NR' 2

-NR'

2

CH(OR')

2 -0(CH2)m-CH(OR')2, 2 -0 (CH2)mCR"'(OR")2 or by R"0-CHR CHCOR"-(Cl -C 6 )alkoxy, R 51is identical or different halogen, nitro, (Cl-C4)alkoxy and phenyl which is unsubstituted or substituted by one or more, preferably up to three, radicals R 52is identical or different halogen, (Cl-C 4 )alkyl, (Cl-C 4 )alkoxy, (Ci -C4)haloalkyl, (C 1 -C4)haloalkoxy or nitro; R' is identical or different hydrogen, (Cl-C 4 )alkyl, phenyl which is unsubstituted or substituted by one or more, preferably up to three, radicals R 5, or two radicals R' together form a (C 2

-C

6 )alkanediyl chain; R" is identical or different (Ci -C4)alkyl or two radicals R" together form a (C2-C 6 )alkanediyl chain; is hydrogen or (Ci -C4)alkyl; m is0,1, 2, 3, 4, 5or6.

Especially preferred are herbicide/safener combinations according to the invention comprising safener of the formula (11) and/or (1ll) where the symbols and indices have the following meanings: R 24is hydrogen, (Cl-C 8 )alkyl or (C 3

-C

7 )cycloalkyl, the abovementioned carbon-containing radicals being unsubstituted or mono- or polysubstituted by halogen or mono- or disubstituted, preferably monosubstituted, by radicalsR R 0is identical or different hydroxyl, (Ci -C4)alkoxy, carboxyl, (Ci -C4)alkoxycarbonyl, (C 2

-C

6 )alkenyloxycarbonyl, (C2-C6)alkynyloxycarbonyl, 1 -(hydroxyimino)(Ci -C 4 )alkyl, 1 -C4)alkylimino]- (Ci -C4)alkyl and 1 -C 4 )alkoxyimino](Cl -C4)alkyl; -SiR' 3

-O-N=CR'

2

-N=CR'

2

-NR'

2 and -O-NR' 2 in which R' is identical or different hydrogen, (Cl-C4)alkyl or, as a pair, a chain, 97 R R R are identical or different hydrogen, (Ci -C8)alkyl, (Cl-C 6 )haloalkyl, (C3-C 7 )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- [(Ci -C 4 )alkyi]amino, (Ci -C 4 )alkyl, (C 1

-C

4 haloalkyl, (Ci -C4)alkoxy, (Cl -C 4 )haloalkoxy, (Cl -C 4 )alkylthio and (C -C 4 )alkylsulfonyl; R 26is hydrogen, (Ci -C 8 )alkyl, (C 1

-C

8 )haloalkyl, (Ci -C 4 )alkoxy)(Ci -C 4 alkyl, (Ci -C6)hydroxyalkyl, (C3-C 7 )cycloalkyl or tri(Ci -C4)alkylsilyl, 17 19 R ,R are identical or different, halogen, methyl, ethyl, methoxy, ethoxy, (Ci or C2)haloalkyl, preferably hydrogen, halogen or (C 1 or

C

2 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 -C 4 )haloalkyl; n' is0, 1, 2or 3; R 18is a radical of the formula OR 2 R 24is hydrogen, (Cl-C 8 )alkyl or (C 3 -C7)ycloalkyl, 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, (Ci -C4)alkoxy, (Ci -C4)alkoxycarbonyl, (C 2

-C

6 )alkenyloxycarbonyl, (C2-C6)alkynyloxycarbonyl, 1 -(hydroxyimino)(Ci -C4)alkyl, 1 1

-C

4 )alkylimino](Cl -C4)alkyl, 1 1 -C4)alkoxyimino](Ci -C 4 alkyl and radicals of the formulae -SiR' 3

-O-N=R'

2 -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, (C 4 or

C

5 )alkanediyl; 18 R27, R28, R29 are identical or different hydrogen, (C1-C 8 )alkyl,

(C

1

-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, (C1-C4)alkyl, (C1-C4)alkoxy, nitro, (C1-C4)haloalkyl and (C1-C 4 )haloalkoxy, and R26 is hydrogen, (C1-C)alkyl, (C1-Cs)haloalkyl, (C1-C4)alkoxy-(C 1 -C4)alkyl, (C 1 -C6)hydroxyalkyl, (C3-C7)cycloalkyl or tri(C1 -C4)alkylsilyl.

Very especially preferred safeners are also those of the formula (Ill) in which the symbols and indices have the following meanings: R is halogen or (C1-C4)haloalkyl; n' is 0, 1, 2 or 3, where (R19 is preferably is a radical of the formula OR24 T is CH 2 or CH(COO-(C1-C 3 -alkyl)) and R24 is hydrogen, (C1-C8)alkyl, (C1-Cs)haloalkyl or (C1-C4)alkoxy- (C1-C4)alkyl, preferably (C1-C 8 )alkyl.

Particularly preferred are the safeners of the formula (II) in which the symbols and indices have the following meanings: W is (W1); 177 R17 is halogen or (C1-C2)haloalkyl; n' is 0, 1, 2 or 3, (R17 preferably being 2,4-CI2; R 8 is a radical of the formula OR24 R24 is hydrogen, (C1-C)alkyl, (C1-C4)haloalkyl, (C1 -C4)hydroxyalkyl, (C3-C7)cycloalkyl, (C1 -C4)alkoxy(C1-C4)alkyl or tri(C1 -C2)alkylsilyl, preferably (C1-C4)alkyl; R27 is hydrogen, (Cl-Cs)alkyl, (C1-C 4 )haloalkyl or (C3-C7)cycloalkyl, preferably hydrogen or (C1-C4)alkyl, and R26 is hydrogen, (C1-C8)alkyl, (C1-C4)haloalkyl, (C1 -C4)hydroxyalkyl, (C3-C7)cycloalkyl, (C1 -C4)alkoxy(C1-C4)alkyl or tri(C1 -C2)alkylsilyl, preferably hydrogen or (C1-C4)alkyl.

Also particularly preferred are herbicidal compositions comprising a safener of the formula (II) where the symbols and indices have the following meanings: W is (W2); 17 R is halogen or (C1-C2)haloalkyl; n' is 0, 1, 2 or 3, (R 17)n' preferably being 2,4-C12; 19 R 8is a radical of the formula OR 2 R 24is hydrogen, (Ci -C8)alkyl, (Ci -C 4 haloalkyl, (Cl-C4)hydroxyalkyl,

(C

3

-C

7 )cycloalkyl, (Ci -C4)alkoxy)-C 1 -04-alkyl or tri(Ci -C2)alkylsilyl, preferably (Ci -C4)alkyl, and R 27is hydrogen, (Cl-C 8 )alkyl, (Cl-C 4 )haloalkyl, (C3-C7)cycloalkyl or phenyl, preferably hydrogen or (Ci -C4)alkyl.

Also particularly preferred are safeners of the formula (11) where the symbols and indices have the following meanings: W is (W3); R 7is halogen or (Ci -C2)haloalkyl; n'I is 0, 1, 2 or 3, (R 17)n' preferably being 2,4-Cl 2 R 18is aradical of the formula OR 2 R 24is hydrogen, (Ci -C 8 )alkyl, 1

C-C

4 haloalkyl, (Ci -C4)hydroxyalkyl, (C3-C 7 )cycloalkyl, (Ci -C4)alkoxy(Ci -C4)alkyl or tri(Ci -C2)alkylsilyl, preferably (Ci -C4)alkyl, and R 28is (Ci -C 8 )alkyl or (Ci -C4)haloalkyl, preferably Ci-haloalkyl.

Also particularly preferred are safeners of the formula (11) where the symbols and indices have the following meanings: W is (W4); R 17is halogen, nitro, (Cl-C 4 )alkyl, (Cl-C2)haloalkyl, preferably CF 3 or (Ci -C4)alkoxy; n' is0, 1, 2or 3; R 18is aradical of the formula OR 2 R 24is hydrogen, (Ci -C 4 )alkyl, carboxy(Ci -C 4 )alkyl, (Ci -C4)alkoxycarbonyl(Cl -C 4 )alkyl, preferably (Cl -C 4 )alkoxy-CO-CH 2 (Ci-C4)alkoxy-CO-C(CH 3

HO-CO-CH

2 or HO-CO-C(CH 3 and R 29is hydrogen, (Cl-C 4 )alkyl, (Cl-C4)haloalkyl, (C 3

-C

7 )cycloalkyl or phenyl which is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (Cl-C4)alkyl, (Ci -C4)haloalkyl, nitro, cyano and (Ci -C4)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 of the formula where W (Wi) and (R 17)n' 2,4-012), preferably compounds such as ethyl 1 -(2,4-dichlorophenyl)-5- (ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (I1-i, mefenpyr-diethyl), and related compounds as they are described in WO-A 91/07874; b) dichlorophenylpyrazolecarboxylic acid derivatives of the formula where W (W2) and (R 17)n' 2,4-012), preferably compounds such as ethyl 1 ichlIo rop he nyl)-5- methyl pyrazole-3-carboxy late ethyl 1 -(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate ethyl 1 -(2,4-dichlorophenyl)-5-( 1,1 -dimethylethyl)pyrazole-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 (W3) and (R 17)n' 2,4-02), preferably compounds such as fenchlorazol-ethyl, i.e. ethyl 1 -(2,4-dichlorophenyl)richlIoromethyl- (1 1, 2,4-triazolIe-3-ca rboxylate 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-dichlorobenzyl)-2-isoxazoline-3-carboxylate (11-7) or ethyl nyl-2-isoxazoIin e-3-carboxyl ate (11-8) and related compounds as they are described in WO-A-91/08202, or of the ethyl iphe nyl-2- isoxazol ineca rboxyl ate type (11-9, isoxadifen-ethyl), the n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate type (11-10) -or the ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate type (11-1 as they are described in WO-A-95/07897.

e) Compounds of the 8-quinolinoxyacetic acid type, for example those of the formula (1ll), where (R 19)n' 5-Cl, R 20= OR 24and T OH 2 preferably the compounds 1 -methylhexyl (5-chloro-8-quinolinoxy)acetate (1ll-i, cloquintocetmexyl), 1 ,3-dimethylbut- 1-yI (5-chloro-8-quinolinoxy)acetate (111-2), 4-allyloxy-butyl (5-ch loro-8-q u inol inoxy) acetate (111-3), 1 -allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (111-4), ethyl (5-ch loro-8-q u inol inoxy) acetate (111-5), methyl (5-chloro-8-quinolinoxy)acetate (111-6), allyl (5-chloro-8-qu inol i noxy) acetate (111-7), 2-(2-propylideneiminoxy)- 1-ethyl (5-chloro-8-quinolinoxy)acetate (111-8), 2-oxoprop- l-yI (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 19 20 24 the formula (1ll), where (R 5-Cl, R OR 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-dichloroacetyl-3,4-dihydro-3-methyl-2H-1 ,4-benzoxazine (IV-1, benoxacor, disclosed in EP 0 149 974), Ni, N2-diallyl-N2-dichloroacetylglycinamide (DKA-24, disclosed in HU 2143821), 4-d ich loroacetyl-l1-oxa-4-aza-spi ro[4 ,5]decane (AID-67), 2,2-d ichlIo ro-N-(1 ,3-d ioxolan -2-yl methyl) -N rope nyl)acetamnide (PPG-1 292), 3-dichloroacetyl-2,2,5-trimethyloxazolidine, 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine, 3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine, 3-dichloroacetyl-5-(2-fu ranyl)-2,2-dimethyloxazolidine (fu rilazole, MON 13900), 1 -dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1 ,2-a]pyrimidine- 6(2H)-one (dicyclonon, BAS 145138), h) compounds of group preferably 1 ,8-naphthalic anhyd ride, me~hyl 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 ich lo romethyl-2-methyl- 1, 3-d ioxolIan (MG-i 91), N-(4-methylphenyl)-N'-( 1-methyl-i -phenylethyl)urea (dym ron), 1 -[4-(N-2-methoxybenzoylsu Ifamoyl)phenyl]-3-methylurea, 1 -[4-(N-2-methoxybenzoylsuIf amoyl)phenyl]-3,3-dimethylu rea, 1 -[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylu rea, 1 nap hthoyls ulfamoyl) phe nyl]-3,3-d imethyl urea, (2,4-d ich lo rophen oxy) acetic acid (h -1 (4-chlIo rophenoxy) acetic acid, (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (h mecoprop), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-ch lo ro-o-tolyloxy) acetic acid (h MCPA), 4-(4-chloro-o-tolyloxy)butyric acid, 4-(4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoic acid (dicamba), 1 -(ethoxycarbo nyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichior) and their salts and esters, preferably (Cl-C 8 Furthermore preferred as safeners, are compounds of the formula or their salts, where R 0is hydrogen, (C-C&)akyl, (C 3

-C

6 )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-C4)alkoxy, halo(Cl-C 6 alkoxy and (Ci -C 4 )alkylthio and, in the case of cyclic radicals, also (Ci -C4)alkyl and (Ci -C 4 )haloalkyt, R 31is hydrogen, R 32is halogen, halo(Cl -C 4 )alkyl, halo(Ci -C4)alkoxy, (C 1 -C4)alkyl, (Ci -C 4 )alkoxy, (C 1 -C4)alkylsulfonyl, (Cl -C4)alkoxycarbonyl or (Ci -C 4 )alkylcarbonyl, preferably halogen, (Ci -C 4 )haloalkyl, such as trifluoromethyl, (Ci -C 4 )alkoxy, halo(Ci -C4)alkoxy, (Ci -C4)alkoxycarbonyl or (Ci -C 4 )alkylsulfonyl, R 3is hydrogen, R 4is halogen, (Ci -C 4 )alkyl, halo(C 1 -C4)alkyl, halo(Ci -C4)alkoxy,

(C

3

-C

6 )cycloalkyl, phenyl, (Ci -C 4 )alkoxy, cyano, (Ci -C 4 )alkylthio, (Ci -C 4 )alkylsulfinyl, (Ci -C 4 )alkylsulfonyl, (Ci -C4)alkoxycarbonyl or (Cl -C 4 )alkylcarbonyl, preferably halogen, (Ci -C 4 )alkyl, (Ci -C 4 )haloalkyl, such as trifluoromethyl, halo(C 1

-C

4 )alkoxy, (Ci -C 4 )alkoxy or (Ci -04)alkyith jo, n is 0,l1or 2and mn isl1or 2.

Furthermore preferred are safeners of the formula in which X3 is CH; R 35is hydrogen, (Ci-C~)alkyl, (C3-C 6 )cycloalkyl, (C2-C6)alkenyl,

(C

5

-C

6 )cycloalkenyl, phenyl or 3- to 6-membe red 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, (Ci -C 6 )alkoxy, (Ci -C6)haloalkoxy, (Ci -C 2 )alkylsulfinyl, (Ci -C2)alkylsulfonyl, (C 3

-C

6 )cycloalkyl, (Ci -C 4 )alkoxycarbonyl, (Cl-C 4 )alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (Ci -C4)alkyl and (Ci -C 4 )haloalkyl; R 36is hydrogen, (Cl-C6)alkyl, (C2-C 6 )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, (Ci -C 4 )alkyl, (Ci -C 4 )alkoxy and (Ci -C 4 )alkylthio; R 7is halogen, (Ci -C 4 )haloalkyl, (Ci -C 4 )haloalkoxy, nitro, (Ci -C4)alkyl, (Ci -C4)alkoxy, (Ci -C 4 )alkylsulfonyl, (Ci -C 4 )alkoxycarbonyl or (Ci -C 4 )alkylcarbonyl; R 38is hydrogen; R 9is halogen, nitro, (C 1

-C

4 )alkyl, (Ci -C 4 )haloalkyl, (Ci -C 4 )haloalkoxy,

(C

3 -C6)cycloalkyl, phenyl, (Ci -C4)alkoxy, cyano, (Ci -C 4 )alkylthio, (Ci -C 4 )alkylsulfinyl, (Ci -C 4 )alkylsulfonyl, (Ci -C4)alkoxycarbonyl or (Ci -C 4 )alkylcarbonyl; n is 0,l1or 2and m isl1or 2.

Especially preferred amongst the safeners of the formula (VII) are the subgroups which follow:48 9 compounds in which R and R (Ci -C 8 )alkyl, phenyl, phenyl(Ci -C 8 )alkyl, (Ci -C 4 )alkoxy-(C 1 -C8)alkyl, (C 3

-C

6 )alkenyl or

(C

3

-C

6 )alkynyl, it being possible for phenyl rings to be substituted by F, CI, Br, NO 2 CN, OCH 3 (C1-C 4 )alkyl or CH 3 -S0 2 compounds in which R a

H;

compounds in which A Rb; compounds in which E 0; compounds in which 1 47 47 compounds in which R H; compounds in which m" 1 and E 0 or S; compounds in which m" 0; 44 1 47 compounds in which R 4 to R are H, m" 1, E 0, Q CR 2 and A R in particular those where R 4 7 H, R CH 3 and

Y=O;

1 47 compounds in which Q CR 2 and m" equals 0, in particular 44 47 b b those in which R and R H and A R -Y where R is preferably methyl and Y is preferably O.

Examples of preferred combinations of herbicidal active substances (A) and safeners are: (I 1) (II (I 1) (II (I 1) (III (I 1) (IV (I 1) (h (I 1) (h 2) and (I 1) (h 3).

The safeners (antidotes) of the formulae (II) (VII) and the compounds of group B 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 is 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 present 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 which comprises applying a herbicidally active amount of the herbicidally active 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 of group B can be applied to the plants, plant seeds or the area on which the plants grow before, after or together 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 which display tolerance as a result of selection-based breeding.

The safeners, preferably of the formulae (11) (VII) and/or of group B and the abovementioned herbicidal active substances of the formula can be formulated, together or seperately in various ways, 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, 27 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-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4 th 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; Schonfeldt, "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, or 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 herbicidally 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-Cl )-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 of group B 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 (11) (VII) and/or of group B 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 t h 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, i.e. 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-sodium (KIH-2023), bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butroxydim (ICI-0500), butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, i.e.

2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chloroallyl diethyldithiocarbamate; chlomethoxyfen; chloramben; chloransulam-methyl (XDE-565), chlorazifop-butyl, chlorbromuron; chlorbufam; chlorfenac; chlorflurecolmethyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinidon-ethyl, cinmethylin; cinosulfuron; clethodim; clodinafop and its ester derivatives clod inafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (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; dliclosulam (XIDE-564), diethatyl; difenoxu ron; difenzoquat; diflufenican; diflufenzopyrsodium (SAN-835H), dimefuron; di methachior; dimethametryn; dimethenamid (SAN-582H); dimethazone, 5-(4,6-dimethylpyrimidin-2-ycarbamoylsulfamoyl)- 1 py ridyl)-pyrazole-4-carboxyl ate (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), EPTO; esprocarb; ethalflu ralin; ethametsuIf u ron -m ethyl; ethidimuron; ethiozin; ethofumesate; F523 1, i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluorpropyl)-4,5dihydro-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)-l1-(2,3-dihydro- 1,1 -dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea (EP-A 079 683); 3-(4ethyl-6-methoxy-1 ,3,5-triazin-2-yl)-1 -(2,3-dihydro- 1,1 -dioxo-2methylbenzo[b]thiophene-7-su lfonyl)u rea (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; flufonacet (BAY-FOE-5043), fluazifop and fluazifop-P, florasulam (DE-570) and their esters, e.g. fluazifop-butyl and fluazifop-Pbutyl; fluchloralin; 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 (D PX-KE459), fI undone; flurochloridone; flu roxypyr; flu rtamone; fluthiacet-methyl (KI H-920 fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron and its esters methyl ester, NC-31 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-4iodo-2-[3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)u reidosulfonyl]-benzoate, sodium salt, WO 92/13845); ioxynil; isocarbamid; isopropalin; isoproturon; 32 isou ron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; Iinu ron; MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachior; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metobenzu ron, methyl-2-[3-(4,6-dimethoxypyrimidin-2yI)u reidosulfonyl]-4-methanesulfonamidomethylbenzoate (WO 95/10507); methobenzuron; metobromu ron; metolachior; S-metolachior, metosulamn (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensu Ifate; monolinuron; monu ron; MT 128, i.e. 6-chIo ro- N- (3-ch loro-2- prope nyl) -5-methyl-N -phe nyl-3pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(i -methylethyl)phenylj-2methylpentanamide; N, N-dimethyl-2-13-(4,6-dimethoxypyrimidin-2yI) ureidosulfonyll-4-formylaminobenzamide (WO 95/01344); naproanilide; napropamide; naptalam; INC 310, i.e. 4-(2,4-d ich lo robe nzoyl) -1 benzyloxypyrazole; neburon; nicosu Ifuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norfiurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxaziclomefone (MY-i 00), oxyfluorfen; oxasulfuron (OGA- 277476), paraquat; pebulate; pendimethalin; pentoxazone (KIPP-31 4), perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachior; primisulfuron-methyl; procyazine; prodiamine; proflu ralin; proglinazine-ethyl; prometon; prometryn; propachior; propanil; propaquizafop and its esters; propazine; propham; propisochior; propyzamide; prosulfalin; prosulfocarb; prosulfuron (OGA- 152005); prynachlor; pyraflufen-ethyl (ET-75 pyrazon; pyrazosulfuronethyl; pyrazoxyfen; pyribenzoxim, pyridate; pyriminobac-methyl (KIH-61 27), 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, iLe. 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; sulfometu ron-methyl; sulfosate (ICI-A0224); su Ifosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebuthiu ron; tepraloxidim (BAS-620H), terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e.

N, N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1 H-i ,2,4-triazole- 1carboxamide; thenyichlor (NSK-850); thiazafluron; thiazopyr (Mon-i 3200); thidiazimin (SN-i 24085); thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron, triazofenamide; tribenu ron-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]-lH-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; 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 herbicidally active substance of the formula or of a compound of the formula (II) (VII) and/or from amongst group 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) 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 substance of the formula or of a compound of the formula (II)-(VII) and/or from amongst group. 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 kaolin-containing 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 suspendable in water is obtained by mixing 20 parts by weight of a herbicidal active substance 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°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 substance 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 (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 75 parts by weight of a herbicidal active substance 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), of calcium lignosulfonate 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 substance of the formula or of a compound of the formula (11) (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 (11) (VII) and/or from amongst group B(b) 5 of sodium 2,2'-dinaphthylmethane-6,6'disulfonate 2 of sodium oleoylmethyltaurinate, 1 of polyvinyl alcohol, 17 of calcium carbonate and 50 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 using a scale of 0 to 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, individually or as mixtures, onto the green parts of the plants 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 three weeks under ideal growth conditions, the effect of the products is scored visually by comparison with untreated controls. The results are summarized in Table 1 below.

Table 1: Active Dose Wheat Maize AMARE VERPE VIOTR PHBPU XANOR sub- g a.s./ha stances (1 1) 75 30 40 100 100 100 100 100 19 20 30 100 100 100 100 100 75+37.5 10 35 100 100 100 100 100 (11- 1) 19+9.5 5 20 100 100 100 100 98 75+75 25 (11-9) 19+19 15 10 100 100 100 100 Abbreviations: g a.s./ha AMARE VERPE VIOTR PHBPU

XANOR=

g of active substance per hectare Amarantus retroflexus Veronica persica Viola Tricolor Pharbitis purpurea Xanthium Orientale The terms (11-1) and (11-9) are explained in the description.

As can be seen from the examples, the herbicide-safener combinations according to the invention are capable of controlling a broad spectrum of weeds in a sustained manner, while damage to crop plants as in comparison with the use of the individual herbicides without safener is substantially reduced.

36a Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (5)

1. A herbicidally active composition comprising a mixture of a herbicidally active amount of one or more compounds of the formula (I) X N-1 Is z N, 0 in which X and Y are identical or different and are hydrogen or halogen such as fluorine, chlorine, bromine or iodine, Z is -S-CHR1-COOR 2 in which R is hydrogen or C1-C20-alkyl, preferably C1-C6-alkyl, R 2 is C1-C20-alkyl, C3-C8-cycloalkyl or C1-Clo-alkoxy-C1-Clo-alkyl, preferably C1-C6-alkyl, C4-C6-cycloalkyl or C1-C4-alkoxy- C 1 -C 4 -alkyl, or is -COOR 3 where R 3 is C 1 -C 20 -alkyl, preferably C1-C 6 -alkyl, or Y and Z together form a group -O-CHR 4 -CO-NR 5 which, together with the phenyl ring, forms a ring in which R 4 is hydrogen or C 1 -C2 0 -alkyl, preferably C 1 -C 6 -alkyl, and R 5 is C1-C 20 -alkyl, C 2 -C 20 -alkenyl or C2-C2 0 -alkynyl, preferably C1-C 6 -alkyl, C 3 -C 5 -alkenyl or C 3 -C 5 -alkynyl, and an antidote-effective amount of one or more safeners.

2. A herbicidally active composition as claimed in claim 1, wherein the compound of the formula has the formula (la) x NJ 0 (la) in which X is hydrogen or halogen, preferably fluorine, Y is halogen, preferably chlorine, and 2 Z is as defined in formula and is preferably -S-CH(CH 3 )-COOR or -S-CH 2 -COOR 2 where R 2 is C1-C6-alkyl or C 4 -C6-cycloalkyl.

3. A herbicidally active composition as claimed in claim 1 or 2, where the safener(s) is selected from the group consisting of: a) compounds of the formulae (II) to (IV), (R17)n' W R 18 O T COR2 0 (I11) R21 N R23 (IV) where the symbols and indices have the following meanings: n' is a natural number from 0 to 5, preferably 0 to 3; T is a (Ci or C2)-alkanediyl chain which is unsubstituted or substituted by one or two (Ci-C4)alkyl radicals or by [(C1-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 0, 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), NN N N I~ N/ RZ 7 RV 0R2 -N COOFP (WI) (W2) W) m' is 0 or 1; R17, R19 are identical or different halogen, (C 1 -C 4 )alkyl, (C1-C4)alkoxy, nitro or (C1-C4)haloalkyl; R R0 are identical or different OR24, SR or NR24R25 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 is linked to the carbonyl group in (II) or (III) via the nitrogen atom and which is unsubstituted or substituted by radicals from the group consisting of (C1-C4)alkyl, (C1-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 R24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical preferably having in total 1 to 18 carbon atoms; R25 is hydrogen, (C1-C6)alkyl, (C1-C 6 )alkoxy or substituted or unsubstituted phenyl; R26 is hydrogen, (C1-C 8 )alkyl, (C1-C 8 )haloalkyl, (C1-C 4 )alkoxy- (C1 -C4)alkyl, (C1 -C 6 )hydroxyalkyl, (C3-C12)cycloalkyl or tri- (C1-C4)-alkylsilyl; R27, R 28, R29 are identical or different hydrogen, (C 1 -C)alkyl, (C 1 -C 8 )haloalkyl, (C3-C12)cycloalkyl or substituted or unsubstituted phenyl; R is (C1-C4)alkyl, (C1-C4)haloalkyl, (C2-C4)alkenyl, (C2-C4)- haloalkenyl, (C 3 -C 7 )cycloalkyl, preferably dichloromethyl; R22, R23 is identical or different hydrogen, (C 1 -C4)alkyl, (C 2 -C 4 )alkenyl, (C2-C4)alkynyl, (C1-C4)haloalkyl, (C 2 -C 4 )haloalkenyl, (C1 -C 4 )alkylcarbamoyl-(C1 -C4)alkyl, (C 2 -C 4 )alkenylcarbamoyl- (C1-C4)alkyl, (C1-C 4 )alkoxy-(C1 -C4)alkyl, dioxolanyl-(C1 -C4)alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R 22and R 23together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; b) one or more compounds from the group consisting of: 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-2-ylmethyloxime (fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl-2-chloro-4-trifluoromethyl- 1,3-thiazole-5-carboxylate (flu razole), 2-dichloromethyl-2-methyl-1 ,3-dioxolane (MG-i 91), N-(4-methylphenyl)-N'-( 1-methyl-i -phenylethyl)u rea (dymron), 1 -[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea, 1 -[4-(N-2-methoxybenzoylsu lfamoyl)phenyl]-3,3-dimethylurea, 1 -14-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea, 1 -[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, (2,4-dichlorophenoxy)acetic acid (4-chlorophenoxy)acetic acid, S) -2-(4-chlIo ro-o-tolyloxy) prop ionic acid (mecoprop),

4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), (4-chloro-o-tolyloxy)acetic acid (MC PA), 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 (lactidichlor) and their salts and esters, preferably (01-08); c) N-acylsulfonamides of the formula and their salts, R 3 1 R 33 1 O (R34)m R 3 4- -N a 0(V 0 where R 3 0 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbonthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, each of the last-mentioned 4 radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, carboxamide, sulfonamide and radicals of the formula -Za-R a each hydrocarbon moiety preferably having 1 to 20 carbon atoms and a carbon-containing radical R 3 0 inclusive of substituents preferably having 1 to 30 carbon atoms; R 3 1 is hydrogen or (C1-C4)alkyl, preferably hydrogen, or 31 R and R 3 1 together with the group of the formula -CO-N- are the radical of a 3- to 8-membered saturated or unsaturated ring; 32 R is identical or different halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH 2 SO 2 NH 2 or a radical of the formula -ZbRb; R 3 3 is hydrogen or (C1-C4)alkyl, preferably hydrogen; R 34 is identical or different halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH 2 SO 2 NH 2 or a radical of the formula -Zc-R Ra is a hydrocarbon radical or a heterocyclyl radical, each of the two last-mentioned radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [(C1-C4)alkyl]amino, or is an alkyl radical in which more than one, preferably 2 or 3, nonadjacent CH 2 groups are each replaced by an oxygen atom; Rb,R identical or different are a hydrocarbon radical or a heterocyclyl radical, each of the two last-mentioned radicals being unsubstituted or substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halo(C1-C4)alkoxy, mono- and di[(C1-C4)alkyl]amino, or are an alkyl radical in which more than one, preferably 2 or 3, nonadjacent CH 2 groups are each replaced by an oxygen atom; Z a is a divalent group of the formula -CO-O-, -S02-, -NR*-CO-, -SO2-NR*- or -NR*-SO2-, the bond shown on the right of the divalent group in question being the bond to the radical R a and the R* in the last-mentioned 5 radicals independently of one another being in each case H, (C 1 -C4)alkyl or halo(C1-C4)alkyl; b c Zb,Z independently of one another are a direct bond or a divalent group of the formula -S-CO-, -S02-, -S02-NR*-, -NR*-S02-, -CO-NR*- or -NR*-CO-, the bond shown on the right of the divalent group in question being b c the bond to the radical R or R respectively, and the R* in the last- mentioned 5 radicals independently of one another being in each case H, (C1-C4)alkyl or halo(C 1 -C 4 )alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular 0 or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; d) acylsulfamoylbenzamides of the formula if appropriate in salt form, R 3 N 0 0 SS-N (R 39 )m (VI) R3 1 (R 37 )n R 3 where X 3 is CH or N; R 3 5 is hydrogen, heterocyclyl or a hydrocarbon radical, the two last- mentioned radicals optionally being substituted by one or more, identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl,. carboxyl, CHO, CONH 2 SO 2 NH 2 and Za-R a R 3 6 is hydrogen, hydroxyl, (C1-C6)alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (C 1 -C 6 )alkoxy, (C2-C6)alkenyloxy, the five last-mentioned radicals optionally being substituted by one or more identical or different radicals selected from the group consisting of halogen, hydroxyl, (C1-C4)alkyl, (C1-C4)alkoxy and (C1-C 4 )alkylthio, or R 3 5 and R 3 6 together with the nitrogen atom to which they are attached are a 3- to 8-membered saturated or unsaturated ring; R is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH 2 SO 2 NH 2 or Zb-Rb R 3 8 is hydrogen, (C1-C4)alkyl, (C2-C4)alkenyl or (C2-C4)alkynyl; R 39 is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO, CONH 2 S0 2 NH 2 or ZC-RC; R a is a (C2-C20)alkyl radical whose carbon chain is interrupted once or more by oxygen atoms, or is heterocyclyl or a hydrocarbon radical, the two last-mentioned radicals optionally being substituted by one or more, identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, mono- and di[(C1-C4)alkyl]amino; R b R c identical or different are a (C2-C20)alkyl radical whose carbon chain is interrupted once or more by oxygen atoms, or are heterocyclyl or a hydrocarbon radical, the two last-mentioned radicals optionally being substituted by one or more identical or different radicals selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, (Ci-C4)haloalkoxy, mono- and di[(C1-C4)- alkyl]amino; Z a is a divalent unit selected from the group consisting of O, S, CO, CS, C(0)O, C(0)S, SO, S02, NR d C(O)NR d or SO 2 NRd; b c Z b Z identical or different are a direct bond or a divalent unit selected from the group consisting of O, S, CO, CS, C(0)O, C(0)S, SO, S02, d d d NR S0 2 NR or C(O)NR; Rd is hydrogen, (C1-C4)alkyl or (C1-C4)haloalkyl; N is an integer from 0 to 4, and m, in the event that X is CH, is an integer from 0 to 5 and, in the event that X is N, an integer from 0 to 4; e) compounds of the formula (VII), Q I (E)m' R41 (VII) Q2 PGQ R42 where the symbols and indices have the following meanings: 4 R is H, (C1-C4)alkyl, (C1-C4)alkyl substituted by (C 1 -C 4 )alkyl-X or 4 43 44 (C 1 -C 4 )haloalkyl-X (Ci-C4)haloalkyl, NO 2 CN, -COO-R NR 2 44, SO 2 NR 2 4 or CONR 2 46 44 R 4 1 is H, halogen, (C 1 -C4)alkyl, CF 3 (C1-C4)alkoxy or (C1-C4)halo- R 4 2 Q1, alkoxy; is H, halogen or (C1-C4)alkyl; Q2, E, G are identical or different, -CR 2

47-, NR 4 8 or a group of the formula (VIII), C=CH-O-CR2-(CO)-A (Vllt) with the proviso that c) at least one of the groups Q Q2, E, G is a carbonyl group, that exactly one of this group is a radical of the formula (VIII) and that the group of the formula (VIII) is adjacent to a carbonyl group, and 1) two adjacent groups Q Q E and G cannot simultaneously be oxygen; R a is identical or different H or (Ci-C8)alkyl or the two radicals R a together are (C2-C6)alkylene; A is Rb _y3_ or-NR2 4 9 X 4 is or Y3 is or R b is H, (Cl-C8)alkyl, (C1-C8)haloalkyl, (C1-C4)alkoxy(C1-C8)alkyl, (C3-C6)alkenyloxy(C 1 -C8)alkyl, or phenyl(Ci-C8)alkyl, the phenyl ring optionally being substituted by halogen, (C1-C4)alkyl, CF 3 methoxy or methyl-S(0)p; (C3-C6)alkenyl, (C3-C6)haloalkenyl, phenyl(C3-C6)alkenyl, (C3-C6)alkynyl, phenyl(C3-C6)alkynyl, oxetanyl, furfuryl, tetrahydrofuryl; R is H or (C1-C4)alkyl; R 4 4 is identical or different H, (C1-C4)alkyl, (C1-C4)alkylcarbonyl or the two radicals R 4 4 together are 46 R 4 5 R are independently of one another in each case identical or different H, (C1-C4)alkyl, or the two radicals R 4 5 and/or R 4 6 together are (C4-C5)alkylene, it being possible for one CH 2 group to be replaced by O or S or for one or two CH 2 groups to be replaced by -NRC-; Rc is H or (C1-C 8 )alkyl; R 4 7 is identical or different H, (Cl-Cs)alkyl or the two radicals R 4 7 together are (C 2 -C6)alkylene; R' is H, (C1-C 8 )alkyl, substituted or unsubstituted phenyl, or benzyl which is unsubstituted or substituted on the phenyl ring; 49 R is identical or different H, (C1-C8)alkyl, phenyl, phenyl(C1-C8)alkyl, it being possible for a phenyl ring to be substituted by F, CI, Br, NO 2 CN, OCH 3 (Cl-C4)alkyl or CH 3 SO 2 or is (C1-C4)alkoxy- (C1-C 8 )alkyl, (C 3 -C6)alkenyl, (C3-C6)alkynyl, (C3-C 6 )cycloalkyl or two radicals R 4 9 together are (C4-C5)alkylene, it being possible for one CH2 group to be replaced by 0 or S or for one or two CH 2 groups to be replaced by -NRd-; Rd is H or (C1-C4)alkyl; m" is 0 or 1 and p is 0, 1 or 2; inclusive of the stereoisomers and of the salts conventionally used in agriculture. 4. A herbicidally active composition as claimed in one or more of claims 1 to 3, in which the weight ratio herbicide:safener is 1:100 to 100:1. A herbicidally active composition as claimed in one or more of claims 1 to 4, additionally comprising one or more further agrochemical active substances. 6. 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 5 to the harmful plants, the crop plants, the seeds of the plants or the area on which the plants grow. 7. The method as claimed in claim 6, wherein the crop plants are selected from the group consisting of maize, wheat, rye, barley, oats, rice, sorghum, cotton and soya. 8. The method as claimed in claim 6 or 7, wherein the crop plants are transgenic or display tolerance as a result of selection-based breeding. 9. The use of a herbicidally active composition as claimed in one or more of claims 1 to 5 for controlling harmful plants in plant crops. 46 A herbicidally active composition substantially as hereinbefore described with reference to the formulation examples. 11. A method of controlling harmful plants in plant crops substantially as hereinbefore described with reference to the biological examples. 12. The use of a herbicidally active composition as claimed in one or more of claims 1 to 5 as hereinbefore described with reference to the examples. DATED this 4 th day of August 2003 AVENTIS CROPSCIENCE GMBH WATERMARK PATENT TRADE MARK ATTORNEYS 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRALIA 20 P20879AU00 KJS/GHO/SLB *eo ft o