WO2003047343A1

WO2003047343A1 - Herbicidal composition

Info

Publication number: WO2003047343A1
Application number: PCT/EP2002/013616
Authority: WO
Inventors: Willy T. RÜEGG
Original assignee: Syngenta Participations Ag
Priority date: 2001-12-03
Filing date: 2002-12-02
Publication date: 2003-06-12
Also published as: AU2002365631A1

Abstract

Herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprise a) a compound of formula I …or an agronomically acceptable salt of that compound, and b) a synergistically effective amount of one or more compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl difenzoquat. Cyhalofop-butyl, dithiopyr, quinclorac, prodiamie, benefin and trifluralin. The compositions according to the invention may also comprise a safener.

Description

Herbicidal composition

The present invention relates to a novel herbicidal composition that comprises a herbicidal active ingredient combination suitable for the selective control of weeds in crops of useful plants, for example in crops of maize. The invention relates also to a method of controlling weeds in crops of useful plants and to the use of such a novel composition for that purpose.

The compound of formula I

exhibits herbicidal activity. The compound of formula I and the preparation thereof are known, for example, from WO 01/94339.

It has now, surprisingly, been found that a combination of variable amounts of active ingredients, that is to say of an active ingredient of formula I with one or more of the known active ingredients listed below, all of which are known and some of which are also available commercially, exhibits a synergistic action that is capable of controlling, both pre-emergence and post-emergence, the majority of the weeds occurring especially in crops of useful plants.

There is therefore proposed in accordance with the present invention a novel synergistic composition for the selective control of weeds that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of

a) a herbicidally effective amount of the compound of formula

or of an agronomically acceptable salt of that compound, and b) a synergistically effective amount of one or more compounds selected from the compound of formula 2.1

wherein R₅ is CH -OMe, ethyl or hydrogen,

R₅₂ is hydrogen, or R₅₁ and R₅ together are the group -CH=CH-CH=CH- and the compound of formula 2.2

wherein R₅₃ is ethyl, R_M is methyl or ethyl and R₅₅ is -CH(Me)-CH₂OMe, <S>-CH(Me)-CH₂OMe, CH₂OMe or CH₂O-CH₂CH₃; and the compound of formula 2.3

wherein R₅₆ is CH(Me)-CH₂OMe or <S>CH(Me)-CH₂OMe; and the compound of formula 2.4

wherein R₅₇ is chlorine, methoxy or methylthio, R₅₈ is ethyl or isopropyl and R₅₉ is ethyl, isopropyl, -C(CN)(CH₃)-CH₃ or tert-butyl; and the compound of formula 2.5

wherein R₆₀ is ethyl or n-propyl, R₆₁ is COO^' 1/2 Ca⁺⁺, -CH₂-CH(Me)S-CH₂CH₃, the group

or the group and X is oxygen, N-O-CH₂CH₃ or

N-O-CH₂CH=CH-CI; and the compound of formula 2.6

wherein R₆₂ is hydrogen, methoxy or ethoxy, R₆₃ is hydrogen, methyl, methoxy or fluorine, R_&4 is COOMe, fluorine or chlorine, R₆₅ is hydrogen or methyl, Y is methine, C-F or nitrogen, Z is methine or nitrogen and R₆₆ is fluorine or chlorine; and the compound of formula 2.7

wherein R₆₇ is hydrogen or -C(O)-S-n-octyl; and the compound of formula 2.8

wherein R₆s is either bromine or iodine; and the compound of formula 2.9

wherein R₆₉ is chlorine or nitro; and the compound of formula 2.10

wherein R₇₀ is fluorine or chlorine and R₇₁ is -CH₂-CH(CI)-COOCH₂CH₃ or -NH-SO₂Me; and the compound of formula 2.11

wherein R₇₂ is trifluoromethyl or chlorine; and the compound of formula 2.12

wherein R₇₃ is NH₂ or <S>NH₂; and the compound of formula 2.13

wherein Y₂ is nitrogen, methine, NH-CHO or N-Me, Y is nitrogen, methine or C-l, Y₃ is methine, Y₄ is methine or Y₃ and Y₄ together are sulfur or C-CI, Y₅ is nitrogen or methine, Y₆ is methyl, difluoromethoxy, trifluoromethyl or methoxy, Y₇ is methoxy or difluoromethoxy and R₇₄ is CONMe₂, COOMe, COOC₂H₅, trifluoromethyl, CH₂-CH₂CF₃, O-CH₂-CH₂CI or SO₂CH₂CH₃, or sodium salts thereof ("Me" in each case being a methyl group); and the compound of formula 2.13.C

and the compound of formula 2.14

and the compound of formula 2.15

and the compound of formula 2.16

and ammonium, isopropylammonium, sodium and

trimesium salts thereof, and the compound of formula 2.17

and the compound of formula 2.18

and the compound of formula 2.19

and the compound of formula 2.20

and the compound of formula 2.21

and the compound of formula 2.22

and the compound of formula 2.23

and the compound of formula 2.24 n-

and the compound of formula 2.25

and the compound of formula 2.26

and the compound of formula 2.27

and the compound of formula 2.28

α- α- and the compound of formula 2.29

and the compound of formula 2.30

and the compound of formula 2.31

and the compound of formula 2.32

and the compound of formula 2.33

and the compound of formula 2.34

H„N SO-NHCC CH. (2.34), and the compound of formula 2.35

and the compound of formula 2.36

and the compound of formula 2.37 (2.37),

and the compound of formula 2.38 (²-³⁸)>

CH₃ (CH₃)₂N N O and the compound of formula 2.39 (2.39),

and the compound of formula 2.40 ^{Cl NHCON}(^CH3)_{2 (} .40),

,C and the compound of formula 2.41 2~O2,H' (2.41 ),

and the compound of formula 2.42

CH,

(CH₃)₃C -_* " y- NCONHCH₃

N - N and the compound of formula 2.43 (2.43),

and the compound of formula 2.44

and the compound of formula 2.45

and the compound of formula 2.46

and the compound of formula 2.47

and the compound of formula 2.48

and the compound of formula 2.49

HO and the compound of formula 2.50

and the compound of formula 2.51

and the compound of formula 2.52

wherein

R R₂ and R₃ are each independently of the others halogen, nitro, cyano, Cι-C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, C C₄haloalkyl, C₂-C₆haloalkenyl, C₃-C₆cycloalkyl, halo- substituted C₃-C₆cycloalkyl, Ci-Cealkoxyalkyl, CrCealkylthioalkyl, hydroxy, mercapto, CrC₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, Cι-C alkylcarbonyl, CrC alkoxycarbonyl, CrC₄alkylthio, CrC₄alkylsulfinyl, Cι-C₄alkylsulfonyl, amino, CrC₄alkylamino or di(Cι-C - ' alkyl)amino; R and R₅ together are a group

-C-R₆(R7)-O-C-R₈(R_β)-C-Rιo(Rn)-C-Ri2(Ri3)- (Zi),

-C-R₁₄(R₁₅)-C-R₁₆(R₁₇)-O-C-R₁₈(R₁₉)-C-R₂₀(R₂ι)- (Z₂), or

-C-R₂2(R2₃)-C-R2₄(R₂5)-C-R26(R27)-O-C-R28(R29)- (Z₃), wherein Re, R₇, Re, R9, Rio, Rn, R12, R13, ι , R15, R16, Ri7> Rιβ, R19, R20, R21, R22, R23, R2 , R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ are each independently of the others hydrogen, halogen, d-C alkyl or Cι-C₄haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the groups Z^ Z₂ or Z₃ contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the groups Z_{1 ;} Z₂ or Z₃₎ or that alkylene ring bridges at least one ring atom of the groups Z,, Z₂ or Z₃;

G is hydrogen,

-C(X₂)-X₃-R3i, -C(X )-N(R₃₂)-R₃3, -SO₂-R₃₄, an alkali metal, alkaline earth metal, sulfonium or ammonium cation or -P(X₅)(R₃₅)-R₃₆; Xι, X₂, X₃, X und X₅ are each independently of the others oxygen or sulfur; and R30, R31, R32, R33, R3 , R35 and R₃₆ are each independently of the others hydrogen, d-Cs- alkyl, CrC₅haloalkyl, C₂-C₅alkenyl, CrC₅alkoxyalkyl, C₃-C₆cycloalkyl or phenyl; and R₃₄ is additionally C₂-C₂₀alkenyl; C₂-C₂₀alkenyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkylalkylcarbonylamino, cyano, (C₃-C₇)cycloalkyl, (C₃-C₇)heterocyclyl, trialkylsilyl, trialkylsilyloxy; phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; C₂-C₂₀alkynyl; C₂-C₂oalkynyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkylalkylcarbonylamino, cyano, (C₃-C₇)cycloalkyl, (C₃-C₇)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; (d-C )cycloalkyl; (Cι-C₇)cycloalkyl substituted by halogen, haloalkyl, (CrC₆)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or by trialkylsilyloxy; heteroaryl; heteroaryl substituted by halogen, haloalkyl, nitro, cyano, (Cι-C₆)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or by trialkylsilyloxy; heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and also salts and diastereo- isomers of the compounds of formula 2.52,

and the compound of formula 2.53

and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalof op-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.

In the above formulae, "Me" is the methyl group.

The invention relates also to the salts that the compound of formula I is able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides suitable as salt formers, attention is drawn to the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially to those of sodium or potassium.

Examples of suitable amines for ammonium salt formation that come into consideration are ammonia as well as primary, secondary and tertiary CrC^alkylamines, C^C^ydroxyalkyl- amines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl- butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n- amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butyl- ethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethyl- amine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec- butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary aryl amines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

It is extremely surprising that the combination of the compound of formula I with one or more active ingredients selected from the formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin exceeds the additive action on the weeds to be controlled that is to be expected in principle and thus broadens the range of action of the individual active ingredients especially in two respects: firstly, the rates of application of the individual compounds of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are reduced while a good level of action is maintained. Secondly, the composition according to the invention achieves a high level of weed control also in those cases where the individual substances, in the range of low rates of application, have become useless from the agronomic standpoint. The result is a substantial broadening of the spectrum of weeds and an additional increase in selectivity in respect of the crops of useful plants, as is necessary and desirable in the event of an unintentional overdose of active ingredient. The composition according to the invention, while retaining excellent control of weeds in crops of useful plants, also allows greater flexibility in succeeding crops.

The composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. The composition according to the invention is suitable for all methods of application conventionally used in agriculture, for example pre-emergence application, post-emergence application and seed dressing. The composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, maize and soybeans, as well as for non-selective weed control.

"Crops" are to be understood to mean also those crops which have been rendered tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering.

Preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either a compound of formula 2.2. a

(2.2.a, aRS,1 'S(-)N-(1 '-methyl-2'-methoxyethyl)-N-

chloroacetyl-2-ethyl-6-methylaniline), or the racemic compound of formula 2.2. b or a compound of formula 2.2 wherein R₅₃ is

ethyl, R_&4 is methyl and R₅₅ is ethoxymethyl, or a compound of formula 2.2 wherein R₅₃ is ethyl, R_M is ethyl and R₅₅ is methoxymethyl, or a compound of formula 2.3, or a compound of formula 2.30, or a compound of formula 2.4, or a compound of formula 2.13, or a compound of formula 2.14, or a compound of formula 2.6 wherein R₆₂ is hydrogen, Z is methine, R₆₃ is methyl, Y is nitrogen, R_M is fluorine, R₆5 is hydrogen and R₆₆ is fluorine, or R₆₂ is methoxy, Z is methine, R₆₃ is methoxy, Y is methine, R_M is chlorine, R₆₅ is methyl and R₆₆ is chlorine, or a compound of formula 2.7 wherein R₆₇ is -C(O)-S-n-octyl, or a compound of formula 2.12, or a compound of formula 2.18, or a compound of formula 2.19, or a compound of formula 2.21 , or a compound of formula 2.25, or a compound of formula 2.33, or a compound of formula 2.45 or a compound of formula 2.1.

Especially preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and either a compound of formula 2.2. a

(2.2.a, aRS,1 'S(-)N-(1 '-methyl-2'-methoxyethyl)-N-

chloroacetyl-2-ethyl-6-methylaniline), or the racemic compound of formula 2.2. b

or a mixture of compounds of formulae 2.2.a and 2.2.b in which the compound of formula 2.2.a is present in excess, preferably in a ratio by weight of from 2.5:1 to 3:1 , relative to the compound of formula 2.2. b, or a compound of formula 2.2 wherein R₅₃ is ethyl, R₅₄ is methyl and R₅₅ is ethoxymethyl, or a compound of formula 2.2 wherein R₅₃ is ethyl, R^ is ethyl and R₅₅ is methoxymethyl, or a compound of formula 2.3, or a compound of formula 2.30.

Further especially preferred synergistic mixtures according to the invention comprise as active ingredients a compound of formula I and a compound of formula 2.52a, as indicated in Table 1 :

Table 1 : Compounds of formula 2.52a:

Comp. Ri R3 Phys. Data No. 1.001 CH₃ CH₃ CH3 H m.p. 245°C 1.002 CH₃ CH₃ CH₃ C(O)C(CH₃)₃ m.p. 135- 136°C

1.003 CH₃ CH₃ CH3 C(O)OCH₂CH₃ 1.004 CH₂CH₃ CH₃ CH3 H m.p. 182- 185°C

1.005 CH₂ ₂C^Hπ₃ CH₃ CH₃ C(O)C(CH₃)₃ m.p. 110- 113°C

1.006 CH₂Cπ₃ CH₃ CH₃ C(O)OCH₂CH₃

1.007 CH₂CH₃ CH₃ CH₂Cπ₃ H m.p. 189- 191 °C

1.008 CH₂CH₃ CH₃ CH₂CH₃ C(O)C(CH₃)₃ m.p. 122- 124°C

1.009 CH₂CH₃ CH₃ CH₂CH₃ C(O)OCH₂CH₃ m.p. 114- 116°C

1 .010 CH=CH₂ CH₃ CH_a H m.p. 165- 170°C

1.01 1 CH=CH₂ CH₃ CH₃ C(O)C(CH₃)₃ m.p. 111 - 113°C

1 .012 CH=CH₂ CH₃ CH₂CH₃ H

1.013 CH=CH₂ CH₃ CH=CH₂ H

1.014 CH=CH₂ CH₃ CH=CH₂ C(O)C(CH₃)₃ Comp. Ri R₂ R3 G Phys. Data

No.

1.015 C≡CH CH₃ CH₃ H m.p. 179- 184°C

1.016 C≡CH CH₃ CH₃ C(O)C(CH₃)₃ m.p. 109- 111 °C

1.017 C≡CH CH₃ CH₃ C(O)OCH₂CH₃

1.018 C≡CH CH₃ CH₂CH₃ H m.p. 189- 193°C

1.019 C≡CH CH₃ CH₂CH₃ C(O)C(CH₃)₃

1.020 C≡CH CH₃ CH2CH₃ C(O)OCH₂CH₃

1.021 C≡CH CH₃ C≡CH H m.p. 300°C

1.022 C≡CH CH₃ C≡CH C(O)C(CH₃)₃ m.p. 183- 185°C

1.023 C≡CH CH₃ C≡CH C(O)OCH₂CH₃

1.024 C≡CH CH₃ CH=CH₂ H

1.025 C≡CCH₃ CH₃ CH₃ H m.p. 179- 181 °C

1.026 C≡CCH₃ CH₃ CH₃ C(O)C(CH₃)₃ m.p. 128- 129°C

1.027 C≡CCH₃ CH₃ CH₃ C(O)OCH₂CH₃

1.028 C≡CCH₃ CH₃ CH₂CH₃ H

1.029 C≡CCH₃ CH₃ CH₂CH₃ C(O)C(CH₃)₃

1.030 C≡CCH₃ CH₃ C≡CCH₃ H

1.031 C≡CCH₃ CH₃ C≡CCH₃ C(O)C(CH₃)₃

1.032 CH₂CH2CH3 CH₃ CH₃ H m.p. 136- 138°C

1.033 CH₂CH₂CH₃ CH₃ CH₃ C(O)C(CH₃)₃ m.p. 65- 67°C

1.034 CH₂CH₂CH₃ CH₃ CH₃ C(O)OCH₂CH₃

1.035 CH₂CH₂CH₃ CH₃ CH2CH3 H

1.036 CH2CH2 1-I₃ CH₃ CH₂CH₂Cπ3 H

1.037 CH2CH2CH3 CH₃ CH₂CH₂CH₃ C(O)C(CH₃)₃ Comp. Ri R₂ R₃ G Phys. Data

No.

1.038 CH₂CH₂Cπ₃ CH₃ CH2CH2CH3 C(O)OCH₂CH₃

1.039 CH₂CH₂CH₃ CH₃ C≡CH H

1.040 CH(CH₃)₂ CH₃ CH₃ H m.p. 214- 216°C

1.041 CH(CH₃)₂ CH₃ CH, C(O)C(CH₃)₃ m.p. 148- 151°C

1.042 CH(CH₃)_Z CH₃ CH₂CH₃ H

1.043 CH(CH₃)₂ CH₃ CsCH H

1.044 t>- CH₃ CH₃ H

1.045 0- CH₃ CH₂CH₃ H

1.046 O- CH₃ C≡CH H

1.048 CH₂CH=CH CH₃ CH₂CH₃ H

1.049 CH₂CH=CH₂ CH₃ C≡CH H

1.050 CH₂CH₂CH₂CH₃ CH₃ CH₃ H

1.051 CH2CH2CH₂CH₃ CH₃ CH₂CH₃ H

1.052 N(CH₂CH₃)₂ CH₃ CH₃ H

1.053 N(CH₂CH₃)₂ CH₃ CH₂CH₃ H

1.054 CH₂OH CH₃ CH₃ H

1.055 CH₂OCH₃ CH₃ CH₃ H

1.056 CH₂OC(CH₃)₃ CH₃ CH₃ H

1.057 CH₃ CH₂CH₃ CH₃ H

1.058 CH₂CH₃ CH₂CH₃ CH₃ H

1.059 CH₂CH₃ CH₂CH₃ CH₂CH₃ H m.p. 185- 187°C

1.060 CH₂CH₃ CH₂CH₃ CH₂CH₃ C(O)C(CH₃)₃ m.p. 6- 128°C Comp. Ri R₂ R₃ G Phys. Da

No.

1.061 CH CH₃ CH₂CH₃ CH₂CH₃ C(O)OCH₂CH₃ m.p. 105 107°C

1.062 CH=CH₂ CH₂CH₃ CH=CH₂ H

1.063 C≡CH CH₂CH₃ C≡CH H

1.064 CH₃ CH=CH₂ CH₃ H

1 .065 CH₂CH₃ CH=CH₂ CH₂CH₃ H

1 .066 CH₂CH₃ CH=CH₂ CH₃ H

1 .067 CH₂CH₃ CH=CH₂ CH₃ C(O)C(CH₃)₃ m.p. 108- 110°C

1 .068 C≡CH CH=CH₂ C≡CH H

1.069 CH₃ C≡CH CH₃ H

1.070 CH₂CH₃ C≡CH CH₃ H m.p. 240- 243°C

1.071 CH₂CH₃ C≡CH CH₃ C(O)C(CH₃)₃ m.p. 138- 140°C

1.072 CH₂CH₃ C≡CH CH₃ C(O)OCH₂CH₃

1 .073 CH CH₃ C≡CH CH₂CH₃ H

1 .074 CH₂CH₃ C≡CH C≡CH H

1 .075 C≡CH C≡CH C≡CH H

1 .076 CH₃ CH₂CH=CH₂ CH₃ H

1 .077 CH₃ CH₂CH=CH₂ CH CH₃ H

1.078 CH₃ CH₃ Br H m.p. 234- 237°C

1.079 CH₃ CH₃ Br C(O)C(CH₃)₃ m.p. 76- 78°C

1 .080 CH₃ CH₃ Br C(O)OCH₂CH₃

1.081 CH₂CH₃ CH₃ Br H

1.082 C≡CH CH₃ Br H

1.083 CH₃ Br CH₃ H m.p. 298- 299°C

1.084 CH₂CH₃ Br CH₃ H m.p. 261 - ^•z. o o o o o o O o o o O o o o o b p o

— - O o o o O O o o o o CD CD CD O CO CO CO O O CO 00 00 00 00 00 o CD 00 -si π cn A CO > o CD 00 -si CD αi O ro O O 00 -si σ> n 3

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o O O O D0 O D0 O O O O TI O O O O O DO DO O O O DO 00 DO

X X X ^{- "}" — -^■ X — — X - - - x x - ^ X X X ^{"■ "•}

O x x x x x x x x x x x x x x x x x x o O X X o o o O o o o o O o o o o o o

X X o o

X X o X o o

X X

Comp. Ri R₂ R3 G Phys. Data

No.

1 .112 OCH₃ CH₃ CH₂CH₃ C(O)OCH₂CH₃

1 .1 13 OCH3 CH₃ CH₂CH₂CH₃ H

1 .114 OCH₃ CH₃ C≡CH H

1 .115 OCH₃ CH₃ Br H

1 .117 C(O)CH₃ CH₃ CH₃ H solid

1.118 C(O)CH₃ CH₃ CH CH₃ H

1.119 CH₃ C(O)CH₃ CH₂CH₃ C(O)C(CH₃)₃ m.p. 163- 165°C

1.120 CH₃ CH₂OH CH₂CH₃ H

1.121 CH₃ CH₃ CH₃ SO₂CH₂CHCH₂

1.122 CH₃ CH₃ CH₃ SO≥CH≥CHCHCI

1 .123 CH₃ CH₃ CH₃ SO2CH2CHCHCH3

1.124 CH₂CH₃ CH₃ CH₂CH₃ SO₂CH₂CHCH₂

1 .125 CH₂CH₃ CH₃ CH₂CH₃ SO₂CH₂CHCHCI

1.126 CH₂CH₃ CH₃ CH₂CH₃ SO2CH2CHCHCH3

Compositions that have proved to be especially effective are combinations of the compound of formula I with the compound of formula 2.2a

(2.2a, aRS,1 'S(-)N-(1'-methyl-2^,-methoxyethyl)-N-

chloroacetyl-2-ethyl-6-methylaniline).

Compounds of formulae 2.1 and 2.3 to 2.13.C are known under the names imazamox, imazethapyr, imazaquin, imazapyr, dimethenamid, atrazine, terbuthylazine, simazine, terbutyrn, cyanazine, ametryn, terbumeton, prohexadione calcium, sethoxydim, clethodim, tepraloxydim, flumetsulam, metosulam, pyridate, bromoxynil, ioxynil, sulcotrione, carfentrazone, sulfentrazone, isoxaflutole, glufosinate, primisulfuron, prosulfuron, rimsulfuron, halosulfuron, nicosulfuron, ethoxysulfuron, flazasulfuron, triasulfuron, tralkoxydim, chlorsulfuron and thifensulfuron-methyl and are described under the entry numbers 412, 415, 414, 413, 240, 34, 692, 651 , 693, 168, 20, 691 , 595, 648, 146, 49, 339, 495, 626, 88, 425, 664, 112, 665, 436, 382, 589, 613, 644, 389, 519, 287, 325, 723, 717, 139 and 704 in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997. The compound of formula 2.13 wherein Y₂, Y3 and Y₄ are methine, Y^ is C-l, R₇₄ is COOMe, Y₅ is nitrogen, Y₆ is methyl and Y₇ is methoxy, is known under the name iodosulfuron (especially the sodium salt) from AGROW No. 296, 16th January 1998, page 22. The compound of formula 2.13 wherein Y_{1 ;} Y₂, Y3 and Y₄ are methine, R₇₄ is trifluoromethyl, Y₅ is nitrogen, Y₆ is trifluoromethyl and Y₇ is methoxy is known under the name tritosulfuron and described in DE-A-40 38 430. The compound of formula 2.13, wherein Y₂ is C-NH-CHO, Yι, Y₃ and Y₄ are methine, R₇₄ is CONMe₂, Y5 is methine and Y₆ and Y₇ are methoxy is known under the name foramsulfuron and described, for example, in WO 95/29899.

The compound of formula 2.13 wherein Y₂ is C-CH₂-NH-SO₂CH₃, Y,, Y₃ and Y₄ are methine, R ₄ COOMe, Y₅ is methine and Y₆ and Y₇ are methoxy is known under the name meso- sulfuron and described, for example, under the Chemical Abstracts Registry Number 208465-21 -8. Dichlorprop is described under the Chemical Abstracts Registry Number 15165-67-0. The S enantiomer of the compound of formula 2.12 is registered under CAS-Reg.No. [35597-44-5]. The compound of the general formula 2.2, aRS,1'S(-)N-(1 '- methyl-2'-methoxyethyl)-N-chloroacetyl-2-ethyl-6-methylaniline, and a compound of the general formula 2.3, (1 S,aRS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1 - methylethyl)-acetamide, are described, for example, in WO 97/34485. The compound of formula 2.9 wherein R₆₉ is NO₂ is known under the name mesotrione and described, for example, in US-A-5 006 158. The compound of formula 2.6 wherein R₆₂ is ethoxy, R₆₃ is fluorine, Y is methine, R_M is methoxycarbonyl, R₆₅ is hydrogen and R₆₆ is chlorine is known under the name cloransulam, for example from AGROW No. 261 , 2nd August 1996, page 21. The compound of formula 2.6 wherein R₆₂ is methoxy, R₆₃ is hydrogen, Y is C-F, R^ is fluorine, R₆₅ is hydrogen and R₆₆ is fluorine is known under the name florasulam and described in US-A-5 163 995.

The following compounds of the composition according to the invention are described in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997: Compound of formula and/or name Pesticide Manual eleventh ed., entry No.:

2.14 (metribuzin) 497

2.15 (aclonifen) 8

2.16 (glyphosate) 383

2.17 (bentazone) 65

2.18 (pendimethalin) 557

2.19 (dicamba) 210

2.20 (butylate) 100

2.22 (clomazone) 150

2.23 (2,4-D) 192

2.24 (flumiclorac) 340

2.25 (fluthiacet-methyl) 359

2.26 (flurtamone) 356

2.27 (flumioxazin) 341

2.28 (paraquat) 550

2.29 (azafenidin) 37

2.30 (fluthiamide) 51

2.33 (sulfosate) 383

2.34 (asulam) 33

2.35 (norflurazon) 526

2.36 (terbacil) 689

2.37 (thiazopyr) 702

2.38 (dithiopyr) 259

2.39 (hexazinone) 400

2.40 (diuron) 260

2.41 (MCPA) 455

2.42 (mecoprop) 459

2.43 (tebuthiuron) 683 prosulfocarb 612 pyraflufen-ethyl 617 fenoxaprop-P-ethyl 309 diclofop-methyl 219 amidosulfuron 21 flupyrsulfuron 348 Compound of formula and/or name Pesticide Manual eleventh ed., entry No flupyrsulfuron-methyl-sodium 348 metsulfuron-methyl 498 sulfosulfuron 668 tribenuron-methyl 728 imazamethabenz-methyl 411 chlorotoluron 134 isoproturon 433 methabenzthiazuron 477 bifenox 69 fluoroglycofen-ethyl 344 imazosulfuron 416 diflufenican 232 bilanafos 71 ethalfluralin 279 trifluralin 740 fluthiamid 51 isoxaben 435 triallate 722

2,4-DB 199

MCPB 457 clopyralid 153 fluroxypyr 354 quinmerac 636 benazolin-ethyl 55 difenzoquat 229 dithiopyr 259 quinclorac 635 prodiamine 593 benefin 57

The following compounds of the composition according to the invention are described in the Pesticide Manual, 12th ed., British Crop Protection Council, 2000:

The compound of formula 2.7 wherein R₆7 is hydrogen, and the preparation thereof, are described in US-A-3 790 571 , the compound of formula 2.6 wherein R₆₂ ethoxy, Z is nitrogen, R₆₃ is fluorine, R^ is chlorine, R₆₅ is hydrogen and R₆₆ is chlorine is described in US-A-5 498 773. The compound of formula 2.21 and the preparation thereof are described in US-A-5 183 492, the compound of formula 2.22 is described under the name isoxachlortole in AGROW No. 296, 16th January 1998, page 22. The compound of formula 2.31 is described under the name fentrazamide in The 1997 British Crop Protection Conference - Weeds, Conference Proceedings Vol. 1 , 2-8, pages 67 to 72; the compound of formula 2.32 is described under the name JV 485 (isoxapropazol) in The 1997 British Crop Protection Conference - Weeds, Conference Proceedings Vol. 1 , 3A-2, pages 93 to 98. The compound of formula 2.44 is known under the name pethoxamid and described, for example, in EP-A-0 206 251. The compound of formula 2.45 is known under the name procarbazone and described, for example, in EP-A-0 507 171 ; the compound of formula 2.46 is known under the name fluazolate and described, for example, in US-A-5 530 126. The compound of formula 2.47 is known under the name cinidon-ethyl and described, for example, in DE-A-40 37 840. The compound of formula 2.48 is known under the name benzfendizone and described, for example, in WO 97/08953. The compound of formula 2.49 is known as diflufenzopyr and described, for example, in EP-A-0 646 315. The compound of formula 2.50 (amicarbazone) and the preparation thereof is disclosed in DD 298 393 and in US-A-5 194 085. The compound of formula 2.51 (flufenpyr-ethyl) is described in Abstracts of Papers American Chemical Society, (2000) Vol. 220, No. Part 1 , pp. AGRO 174. The compounds of formula 2.52 are described in WO 01/17352, and the compound of formula 2.53 is described in US-A-4 881 966. It is extremely surprising that the combination of the compound of formula I with one or more active ingredients selected from formulae 2.1 to 2.53 and from the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin exceeds the additive action on the weeds to be controlled that is to be expected in principle and thus broadens the range of action of the individual active ingredients especially in two respects: firstly, the rates of application of the individual compounds of formulae I and 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are reduced while a good level of action is maintained. Secondly, the composition according to the invention achieves a high level of weed control also in those cases where the individual substances, in the range of low rates of application, have become useless from the agronomic standpoint. The result is a substantial broadening of the spectrum of weeds and an additional increase in selectivity in respect of the crops of useful plants, as is necessary and desirable in the event of an unintentional overdose of active ingredient. The composition according to the invention, while retaining excellent control of weeds in crops of useful plants, also allows greater flexibility in succeeding crops.

The composition according to the invention comprises the compound of formula I and one or more compounds selected from the formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin in any desired mixing ratio, usually with an excess of one of the components over the others. The mixing ratio (ratio by weight) of the compound of formula with the mixing partners of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl- sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is generally from 1 :2000 to 2000:1 , especially from 200:1 to 1 :200.

The rate of application may vary within wide limits and depends on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed to be controlled, the prevailing climatic conditions and other factors governed by the method of application, the time of application and the target crop. The active ingredient mixture according to the invention can generally be applied at a rate of from 1 to 5000 g of active ingredient mixture/ha.

The mixtures of the compound of formula I with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, may be used in unmodified form, that is, as obtained in synthesis. Preferably, however, they are formulated in customary manner, together with the adjuvants conventionally used in formulation technology, such as solvents, solid carriers or surfactants, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, suspensions, suspoemulsions, wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures comprising the compound of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and also, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in a manner known perse, e.g. by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485, page 6.

Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485, pages 7 and 8.

Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81.

The compositions according to the invention may additionally comprise an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives.

In the composition according to the invention, the amounts of oil additive employed are generally from 0.01 to 2 %, based on the spray liquor. The oil additive can, for example, be added to the spray tank in the desired concentration after the spray liquor has been prepared.

Preferred oil additives comprise mineral oils or an oil of vegetable origin such as, for example, rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhόne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin such as, for example, the methyl derivatives, or an oil of animal origin such as fish oil or beef tallow. Especially preferred is the "additive type A", which contains as active components essentially 80 % by weight of alkyl esters of fish oils and 15 % by weight of methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of higher fatty acids (C₈-C₂2), especially the methyl derivatives of C₁₂-Cι₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary company Cognis GmbH, DE).

The application and action of the oil additives can be improved by combining them with surface-active substances such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed in WO 97/34485 on pages 7 and 8.

Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland).The concentration of the surface-active substances based on the total additive is generally from 1 to 30 % by weight.

Surface-active substances the use of which is likewise preferred are silicone surfactants, especially polyalkyl oxide-modified heptamethyltrisiloxanes, such as are obtainable commercially as, for example, Silwet L-77®, and also perfluorinated surfactants.

Examples of oil additives consisting of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) or, more especially, Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can, furthermore, bring about a further increase in action. Suitable solvents are, for example Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation) types. The concentration of those solvents can be from 10 to 80 %, by weight, of the total weight. Such oil additives, which are also described, for example, in US-A-4 834 908, are especially preferred for the composition according to the invention. An especially preferred oil additive is known under the name MERGE®, can be obtained from the BASF Corporation and is basically described, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada).

In addition to the above-listed oil additives, formulations of alkylpyrrolidones such as are marketed commercially, for example as Agrimax®, may additionally be added to the spray liquor in order to increase the action of the compositions according to the invention. There may likewise be used, for the purpose of increasing action, formulations of synthetic latices, for example polyacrylamide, polyvinyl compounds or poly-1 -p-menthene, such as are available on the market as, for example, Bond®, Courier® or Emerald®. In addition, propionic acid-containing solutions, such as Eurogkem Pen-e-trate®, may be added to the spray liquor as action-increasing agents.

One or more of the above-listed oil additives, or of the above-listed formulations of alkylpyrrolidones, synthetic latices or propionic acid-containing solutions, are preferably added to the compositions according to the invention comprising the compounds of formulae 2.52.

The herbicidal formulations generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising the compound of formula I with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron- methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will usually preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. Preferred formulations have especially the following compositions (% = percent by weight):

Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %

Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %

Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples illustrate the invention further, without limiting the invention.

F1. Emulsifiable concentrates i) b) c) d) active ingredient mixture 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %

(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %

(7-8 mol of ethylene oxide) cyclohexanone . - - 10 % 20 % aromatic C₉-C₁₂hydrocarbon mixture 85% 78% 55% 16%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient mixture 5% 10% 50% 90%

1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% - polyethylene glycol MW 400 20% 10% . _

N-methyl-2-pyrrolidone - - 30% 10% aromatic C₉-C₁₂hydrocarbon mixture 75 % 60 %

The solutions are suitable for application in the form of micro-drops.

F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalenesulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% -

(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35% -

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground ih a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93 % 83 %

(diameter 0.1 - 1 mm) for example CaCO₃ or SiO₂

The active ingredient is dissolved in methylene chloride, the solution is applied to the carrier by spraying, and the solvent is subsequently evaporated off in vacuo.

F5. Coated granules a) b) C) active ingredient mixture 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0 % 92% 80%

(diameter 0.1 - 1 mm) for example CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier material moistened with polyethylene glycol, yielding non-dusty coated granules.

F6. Extruder granules a) b) c) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%

The active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and then dried in a stream of air.

F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5% talcum 39.9 % 49% 35% kaolin 60.0 % 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) active ingredient mixture 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2 % -

(15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %

37 % aqueous formaldehyde solution 0.2 % 0.2 % 0.2 % 0.2 % silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

It is often more practical for the compound of formula I and the mixing partners or partner of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin to be formulated separately and then to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application.

The compositions according to the invention may additionally also comprise growth regulators, such as, for example, trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421 ), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). Fungicides, such as, for example, azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311 ), fenpropidin (313), fenpropimorph (314), ferimzone (321 ), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441 ), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591 ), propiconazole (607), pyrazophos (619), pyroquilon (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701 ), thifluzamide (705), triadimefon (720), triadimenol (721 ), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751), may also be present in the compositions according to the invention. The number in parentheses after each active ingredient indicates the entry numbers of those active ingredients in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997.

Biological Examples:

A synergistic effect exists whenever the action of the active ingredient combination of the compound of formulae I and 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is greater than the sum of the actions of the active ingredients applied separately.

The herbicidal action to be expected We for a given combination of two herbicides can be calculated as follows (see COLBY, S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22, 1967):

wherein:

X = percentage herbicidal action on treatment with the compound of formula I at a rate of application of p kg per hectare, compared with the untreated control (= 0 %).

Y = percentage herbicidal action on treatment with a compound of formulae 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin at a rate of application of q kg per hectare, compared with the untreated control.

We = expected herbicidal action (percentage herbicidal action compared with the untreated control) following treatment with the compounds of formulae I and 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin at a rate of application of p + q kg of active ingredient per hectare.

When the action actually observed is greater than the value to be expected We, there is a synergistic effect.

The synergistic effect of the combinations of the compound of formula I with the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is demonstrated in the following Examples. Experiment description - pre-emergence test

Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Directly after sowing, the test compounds are applied in the form of an aqueous suspension by spraying (500 litres of water/ha). The rates of application depend on the optimum concentrations ascertained under field conditions and greenhouse conditions. The test plants are then grown in the greenhouse under optimum conditions. The tests are evaluated after 36 days (% action, 100 % = plant has died, 0 % = no phytotoxic action). The mixtures used in this test show good results.

Experiment description - post-emergence test

The test plants are grown to the 2- to 3-leaf stage in plastics pots under greenhouse conditions. A standard soil is used as cultivation substrate. At the 2- to 3-leaf stage, the herbicides are applied to the test plants on their own and as a mixture. The application is carried out using an aqueous suspension of the test compounds in 500 litres of water/ha. The rates of application depend on the optimum doses ascertained under field conditions and greenhouse conditions. The tests are evaluated after 33 days (% action, 100 % = plant has died, 0 % = no phytotoxic action). In this test, too, the mixtures used show good results. Examples are given in the following Table B1 : Table B1 : Post-emergence action:

It has been shown, surprisingly, that particular safeners are suitable for mixing with the synergistic composition according to the invention. The present invention accordingly relates also to a selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, especially in crops of maize, that comprises a compound of formula I, one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and a safener (counter-agent, antidote) and that protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, as well as to the use of such a composition in the control of weeds in crops of useful plants.

There is accordingly also proposed in accordance with the invention a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) an amount, effective for herbicide synergism, of the compound of formula I and one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1

and the compound of formula 3.2

and the compound of formula 3.3

thereof and salts and hydrates thereof, and the compound of formula 3.4

and the compound of formula 3.5

and the compound of formula 3.6

and the compound of formula 3.7

and the compound of formula 3.8

and of formula 3.9

CI₂CHCON(CH₂CH=CH₂)₂ (3.9),

and of formula 3.10

and of formula 3.1 1

and of formula 3.12

(3.12) and methyl and ethyl esters thereof and salts thereof,

especially the sodium salt, and of formula 3.13

and of formula 3.14

and of formula 3.15

and of formula 3.16

and of formula 3.17

The invention relates also to a selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of the compound of formula I and b) an amount, effective for herbicide antagonism, of a compound selected from the compounds of formulae 3.1 , 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 3.10, 3.11 , 3.12, 3.13, 3.14, 3.15, 3.16 and 3.17.

Preferred compositions according to the invention comprise as safener a compound selected from the compounds of formulae 3.1 , 3.3 and 3.8. Such safeners are suitable especially for the compositions according to the invention that comprise the above-mentioned preferred compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen- ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.

Preferred compositions according to the invention also comprise an amount, effective for herbicide antagonism, of 2-(5-chloroquinolin-8-yloxy)-1 -methyl hexyl ester of formula 3.3, or a hydrate thereof, especially 1-methylhexyl-(5-chloroquinolin-8-yloxy)acetate tetrahydrate, the free acid thereof or a salt thereof of formula

wherein M is a mono-, di- or tri-valent metal, ammonium, N(R)_{4 or} HN(R)₃, wherein the substituents R are identical to or different from one another and are CrC₁₆alkyl or Cι-C₁₆hydroxyalkyl, or M is S(R_a)₃ or P(R_a) , wherein the substituents R_a are identical to or different from one another and are CrC₂₀alkyl, C₂-C₂₀alkenyl, C₂-C₂₀alkynyl , aryl substituted by CrC₂₀alkyl, C₂-C₂oalkenyl or by C₂-C₂₀alkynyl or heteroaryl substituted by d-C^alkyl, C₂-C₂₀alkenyl or by C₂-C₂₀alkynyl, or 2 substituents R_a together with the sulfur or phosphorus atom to which they are bonded form a 5- or 6-membered ring.

The metal atoms M that may be present in formula 3.3a are preferably those of alkali metals or alkaline earth metals, especially sodium, potassium, calcium, magnesium and also especially aluminium and iron as preferred examples of trivalent metals. Of the alkyl and hydroxyalkyl substituents R, preference is given to those having from 12 to 16 carbon atoms and also to those having from 1 to 4 carbon atoms. The groups N(R)₄ and HN(R)₃ especially contain one long-chain and also 2 or 3 short-chain alkyl groups, such as, for example, hexadecyl-triethylammonium, tetradecyl-triethylammonium, dodecyl- triethylammonium, dodecyl-ethyl-dimethylammonium and also tetradodecylammonium. Preferred alkyl groups R_a contain from 1 to 12, especially from 1 to 6, carbon atoms. The alkyl groups R and R_a may in addition be substituted, for example by halogen, alkoxy or haloalkoxy, each of which preferably has from 1 to 4 carbon atoms. Preferred alkenyl and alkynyl groups R_a contain from 2 to 12 carbon atoms. They may contain more than one unsaturated bond and may be substituted by halogen, alkoxy or haloalkoxy, each of which preferably has from 1 to 4 carbon atoms. Suitable examples of aryl groups R_a are phenyl, naphthyl, tetrahydronaphthyl, indanyl and indenyl, phenyl being preferred. Such groups may be substituted by the above-mentioned alkyl, alkenyl and alkynyl groups. There may be mentioned as heteroaryl groups R_a preferably 5- and 6-membered rings that contain especially nitrogen and/or oxygen atoms, such as, for example, pyridyl, pyrimidinyl, triazinyl, thienyl, thiazolyl, pyrazolyl, imidazolyl, piperidyl, dioxolanyl, morpholinyl and tetrahydrofuryl. Such heterocycles may also in addition be substituted by the above-mentioned alkyl, alkenyl and alkynyl groups. Every 2 R_a substitutents may, together with the sulfur or phosphorus atom to which they are bonded, form a ring. Preferably, 5- or 6-membered rings that are saturated are formed. The sulfonium and phosphonium cations that can be used according to the invention are described, for example, in WO 00/44227.

Preferred salts of 2-(5-chloroquinolin-8-yloxy)-1 -methyl hexyl ester comprise a compound of formula 3.3a wherein M is sodium, potassium or tri(hydroxyethylene)ammonium.

A further group of preferred salts of 2-(5-chloroquinolin-8-yloxy)-1 -methyl hexyl ester comprises those wherein, in formula 3.3a, M is calcium, magnesium, aluminium, iron, trimethylsulfonium, triphenylsulfonium, tetraphenylphosphonium, triphenyl- methylphosphonium, triphenyl-benzylphosphonium, Cι₂-C₁₆alkyl-trimethylammonium, Cι₂-C₁₆alkyl-triethylammonium, tetradodecylammonium or dodecyl-ethyl-dimethylammonium. The salts of formula 3.3a can be prepared according to customary methods, for example by reaction of 2-(5-chloroquinolin-8-yloxy)-1 -methyl hexyl ester with an equimolar amount of a metal hydroxide in alcoholic solution at room temperature.

The salts listed in the following Table are obtainable in that manner: Table A: Compounds of formula 3.3a:

Further preferred compositions according to the invention comprise a compound of formula 2.53 and an amount, effective for herbicide antagonism, of 2-(5-chloroquinolin-8-yloxy)-1- methyl hexyl ester of formula 3.3, or a hydrate thereof, especially 1 -methyl hexyl-(5- chloroquinolin-8-yloxy)acetate tetrahydrate, the free acid thereof or a salt thereof of formula 3.3a.

Combinations of the compound of formula I with the compound of formula 3.1 have proved to be especially effective compositions. Such a composition is used preferably together with the compound of formula 2.2a

(2.2a, aRS,1 'S(-)N-(1 '-methyl-2'-methoxyethyl)-N-

chloroacetyl-2-ethyl-6-methylaniline).

The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a herbicidally effective amount of the herbicide of formula I, optionally one or more herbicides selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron- methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, and an amount, effective for herbicide antagonism, of a safener from formulae 3.1 to 3.17.

The compounds of formulae 3.1 to 3.17 are known and are described, for example, in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under the entry numbers 61 (formula 3.1 , benoxacor), 304 (formula 3.2, fenclorim), 154 (formula 3.3, cloquintocet), 462 (formula 3.4, mefenpyr-diethyl), 377 (formula 3.5, furilazole), 363 (formula 3.8, fluxofenim), 213 (formula 3.9, dichlormid) and 350 (formula 3.10, flurazole). The compound of formula 3.11 is known under the designation MON 4660 (Monsanto) and is described, for example, in EP-A-0 436 483.

The compound of formula 3.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula 3.7 in DE-A-2 948 535. The compounds of formula 3.12 are described in DE-A-4 331 448, and the compound of formula 3.13 in DE-A-3 525 205. The compound of formula 3.14 is known, for example, from US-A-5 215 570, and the compound of formula 3.15 from EP-A-0 929 543. The compound of formula 3.16 is described in WO 99/00020. In addition to the compound of formula 3.16, the remaining 3-(5- tetrazolylcarbonyl)-2-quinolones described in WO 99/00020, especially the compounds specifically disclosed in Tables 1 and 2 on pages 21 to 29, are suitable for protecting crop plants against the phytotoxic action of the compound of formula I. The compound of formula 3.17 is described, for example, in US-A-6 162 762.

As crop plants that can be protected by the safeners of formulae 3.1 to 3.17 against the damaging effect of the above-mentioned herbicides there come into consideration especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, more especially cereals. "Crops" are to be understood to mean also those crops which have been made tolerant to herbicides or classes of herbicides (le.g. HPPD-inhibitors, ALS- inhibitors, EPSPS-(5-enol-pyruvyl-shikimate-3-phosphate-synthease)inhibitors or GS- (glutamine-synthease)inhibitors) as a result of conventional methods of breeding or genetic engineering. Examples for crops which have been made tolerant to imidazolinone as a result of conventional methods of breeding (mutagenese) is Clearf iled® canola. An example for crops which have been made tolerant to herbicides or classes of herbicides as a result of genetic engineering are maize seeds which are resistant to glyphosate and glufosinate respectively, commercially available under the brand Roundup Ready® and Liberty Link®.

The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Agrostis, Digitaria, Avena, Apera, Brachiaria, Phalaris, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Panicum, Bromus, Alopecurus, Sorghum halepense, Sorghum bicolor, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. Areas of cultivation include the areas of ground on which the crop plants are already growing or which have already been sown with the seeds of those crop plants, as well as ground intended for cultivation with such crop plants.

Depending on the intended use, a safener of formulae 3.1 to 3.17 can be used in the pretreatment of the seed of the crop plant (dressing of the seeds or cuttings) or can be introduced into the soil before or after sowing. It can, however, also be applied, either alone or together with the herbicide, after emergence of the plants. The treatment of the plants or seeds with the safener can therefore in principle be carried out independently of the time at which the herbicide is applied. The plants can, however, also be treated by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The ratio of the rate of application of safener to the rate of application of herbicide depends largely on the method of application. In the case of field treatment, which is carried out either using a tank mixture comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicides to safener is generally from 100:1 to 1 :10, preferably from 20:1 to 1 :1. In the case of field treatment it is usual to apply from 0.001 to 1.0 kg of safener/ha, preferably from 0.001 to 0.25 kg of safener/ha.

The rate of application of herbicides is generally from 0.001 to 5 kg/ha, but preferably from 0.005 to 0.5 kg/ha.

The compositions according to the invention are suitable for all methods of application conventionally used in agriculture, e.g. pre-emergence application, post-emergence application and seed dressing.

In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. When the safener is applied in liquid form shortly before sowing, with soaking of the seeds, then advantageously the safener solutions used contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.

For the purpose of application, the safeners of formulae 3.1 to 3.17 or combinations of those safeners with the herbicide of formula I and optionally one or more herbicides selected from formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are advantageously formulated together with adjuvants customary in formulation technology, e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.

Such formulations are described, for example, in WO 97/34485, pages 9 to 13. The formulations are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) can also be used in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, in WO 97/34485, page 6.

Depending on the nature of the compound of formulae I, 2.1 to 2.53 and prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and 3.1 to 3.17 to be formulated, there come into consideration as surface-active compounds non- ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising the compound of formula I, a compound selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop- methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and the compounds of formulae 3.1 to 3.17, further from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products are usually formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. For the use of safeners of formulae 3.1 to 3.17, or of compositions comprising them, in the protection of crop plants against the damaging effects of herbicides of formulae I and 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron- methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin, various methods and techniques come into consideration, such as, for example, the following: i) Seed dressing a) Dressing of the seeds with a wettable powder formulation of a compound from formulae 3.1 to 3.17 by shaking in a vessel until uniformly distributed over the seed surface (dry dressing). In that procedure approximately from 1 to 500 g of compound from formulae 3.1 to 3.17 (4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Dressing of the seeds with an emulsifiable concentrate of a compound from formulae 3.1 to 3.17 according to method a) (wet dressing). c) Dressing by immersing the seeds for from 1 to 72 hours in a liquor comprising from 100 to 1000 ppm of a compound from formulae 3.1 to 3.17 and optionally subsequently drying the seeds (immersion dressing).

Dressing the seed or treating the germinated seedling are naturally the preferred methods of application, because treatment with the active ingredients is directed entirely at the target crop. Generally from 1 to 1000 g of antidote, preferably from 5 to 250 g of antidote, are used per 100 kg of seed, but depending on the methodology, which also allows other active ingredients or micronutrients to be added, concentrations above or below the limits indicated may be employed (repeat dressing).

ii) Application as a tank mixture

A liquid formulation of a mixture of antidote and herbicide is used (ratio by weight of the one to the other from 10:1 to 1 :100), the rate of application of herbicide being from 0.005 to

5.0 kg per hectare. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow

The compound from formulae 3.1 to 3.17 is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. Once the seed furrow has been covered over, the herbicide is applied in the usual manner pre-emergence. iv) Controlled release of active ingredient

The compound from formulae 3.1 to 3.17 is applied in solution to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If desired, it is also possible to apply a coating that allows the active ingredient to be released in metered amounts over a specific period of time (coated granules).

Preferred formulations have especially the following compositions:

(% = percent by weight) Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %

The following Examples illustrate the invention further, but do not limit the invention.

Formulation Examples for mixtures of herbicides of formula I. optionally of formulae 2.1 to 2.53 and the compounds prosulfocarb. picolinafen. pyraflufen-ethyl. beflubutamid. fenoxaprop-P-ethyl. diclofop-methyl. amidosulfuron. flupyrsulfuron. flupyrsulfuron-methyl- sodium. metsulfuron-methyl. sulfosulfuron. tribenuron-methyl. imazamethabenz-methyl. flucarbazone. chlorotoluron. isoproturon. methabenzthiazuron. bifenox. fluoroglycofen-ethyl. imazosulfuron. diflufenican. bilanafos. ethalfluralin. trifluralin. fluthiamide. isoxaben. triallate. 2,4-DB. dichlorprop. MCPA. MCPB. mecoprop. MCPP. mecoprop-P. clopyralid. fluroxypyr. guinmerac. benazolin-ethyl. difenzoguat. cyhalofop-butyl. dithiopyr. guinclorac. prodiamine. benefin and trifluralin and optionally safeners of formulae 3.1 to 3.17 (% = percent by weight)

F1. Emulsifiable concentrates a) b) c) d) active ingredient mixture 5 % 10% 25% 50% calcium dodecylbenzenesulfonate 6 % 8% 6% 8% castor oil polyglycol ether 4 % - 4% 4%

(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %

(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % aromatic C₉-Cι₂ hydrocarbon 85% 78% 55% 16% mixture

Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient mixture 5% 10% 50% 90%

1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% - polyethylene glycol MW 400 2 200 %% 10% _ _

N-methyl-2-pyrrolidone - - 30% 10% aromatic C₉-C₁₂ hydrocarbon 75 % 60 % mixture

The solutions are suitable for use in the form of microdrops.

F3. Wettable powders a) • b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2% _

(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3 % 5 % 10 % kaolin 88% 62% 35%

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) active ingredient mixture 0.1 % 5% 15% highly dispersed silicic acid 0.9 % 2% 2% inorganic carrier 99.0 % 93% 83%

(diameter 0.1 - 1 mm) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol, yielding non-dusty coated granules.

The active ingredient is mixed with the adjuvants, and the mixture is ground, moistened with water, extruded and then dried in a stream of air. F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5 % talcum 39.9 % 49 % 35 % kaolin 60.0 % 50 % 60 %

F8. Suspension concentrates a) b) c) d) active ingredient mixture 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -

37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87 % 79 % 62 % 38 %

It is often more practical for the compounds of formulae I, 2.1 to 2.53, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin and 3.1 to 3.17 to be formulated separately and then to be brought together in the desired mixing ratio in the applicator in the form of a "tank mixture" in water shortly before application. The ability of the safeners of formulae 3.1 to 3.17 to protect crop plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples.

Biological Example: safening action

The test plants are grown in plastics pots under greenhouse conditions to the 4-leaf stage. At that stage, either the herbicides alone or the mixtures of the herbicides with the test compounds being tested as safeners are applied to the test plants. The test compounds are applied in the form of an aqueous suspension prepared from a 25 % wettable powder (Example F3, b)), or a suspension concentrate as in Example F8, using 500 litres of water/ha. 3 weeks after application, the phytotoxic action of the herbicides on the crop plants, e.g. maize and cereals, is evaluated using a percentage scale. 100 % indicates that the test plant has died, 0 % indicates no phytotoxic action. The mixtures according to the invention exhibit a good action in this test. Examples of the good selective herbicidal action are given in the following Table BS1 : Table BS1 : post-emergence selective herbicidal action:

The results in the above Table show that, although the compound of formula I on its own protects the crop plant winter barley at a rate of application of 15 g/ha, it exhibits only moderate herbicidal action against the weed Raphanus. The herbicide of formula 2.53 in conjunction with the safener of formula 3.3 is almost without effect against the weed Raphanus at the tested rate of application but clearly damages the winter barley. The combination of the compound of formula I with the compounds of formulae 2.53 and 3.3 does not exhibit any phytotoxic action on winter barley. At the same time, control of the weed Raphanus is appreciably improved.

Claims

What is claimed is:

1. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of the compound of formula I

wherein R₅ι is CH₂-OMe, ethyl or hydrogen,

R₅₂ is hydrogen, or R₅₁ and R₅₂ together are the group -CH=CH-CH=CH- and the compound of formula 2.2

wherein R₆₀ is ethyl or n-propyl, R₆ι is COO^" 1/2 Ca⁺⁺, -CH₂-CH(Me)S-CH₂CH₃, the group

or the group and X is oxygen, N-O-CH₂CH₃ or

N-O-CH₂CH=CH-CI; and the compound of formula 2.6

wherein R₆₂ is hydrogen, methoxy or ethoxy, R^ is hydrogen, methyl, methoxy or fluorine, R_&4 is COOMe, fluorine or chlorine, R₆s is hydrogen or methyl, Y is methine, C-F or nitrogen, Z is methine or nitrogen and R₆₆ is fluorine or chlorine; and the compound of formula 2.7

wherein R₆₇ is hydrogen or -C(O)-S-n-octyl; and the compound of formula 2.8

wherein R₆₈ is either bromine or iodine; and the compound of formula 2.9

wherein R₆g is chlorine or nitro; and the compound of formula 2.10

wherein R₇₀ is fluorine or chlorine and R₇ι is -CH₂-CH(CI)-COOCH₂CH₃ or -NH-SO₂Me; and the compound of formula 2.1 1

wherein R₇₃ is NH₂ or <S>NH₂; and the compound of formula 2.13

wherein Y₂ is nitrogen, methine, NH-CHO or N-Me, Y-_t is nitrogen, methine or C-l, Y₃ is methine, Y₄ is methine or Y₃ and Y₄ together are sulfur or C-CI, Y₅ is nitrogen or methine, Y₆ is methyl, difluoromethoxy, trifluoromethyl or methoxy, Y₇ is methoxy or difluoromethoxy and R₇₄ is CONMe₂, COOMe, COOC₂H₅, trifluoromethyl, CH₂-CH₂CF₃, O-CH₂-CH₂CI or SO₂CH₂CH₃, or a sodium salt thereof ("Me" in each case being a methyl group); and the compound of formula 2.13. c

and the compound of formula 2.14

and the compound of formula 2.15

and the compound of formula 2.16

(2.16), and ammonium, isopropylammonium, sodium and

trimesium salts thereof, and the compound of formula 2.17

and the compound of formula 2.18

and the compound of formula 2.19

and the compound of formula 2.20

and the compound of formula 2.21

and the compound of formula 2.22

and the compound of formula 2.23

and the compound of formula 2.24

n-penty ,r and the compound of formula 2.25

and the compound of formula 2.26

and the compound of formula 2.27

and the compound of formula 2.28

Cl- and the compound of formula 2.29

and the compound of formula 2.30

and the compound of formula 2.31

and the compound of formula 2.32

and the compound of formula 2.33

and the compound of formula 2.34

H₂N S0₂NHC0₂CH„ (2.34), and the compound of formula 2.35

and the compound of formula 2.36 H

and the compound of formula 2.37 2.37),

and the compound of formula 2.38 (²-38),

and the compound of formula 2.39 (2.39),

and the compound of formula 2.40 (2AQ),

and the compoun (2.41),

and the compound of formula 2.42 (₂.42),

CH, ς ' (CH₃)₃C ~ y- NCONHCH₃ and the compound of formula 2.43 ^{N " N} (2.43), and the compound of formula 2.44

and the compound of formula 2.45

and the compound of formula 2.46

and the compound of formula 2.47

and the compound of formula 2.48

and the compound of formula 2.49

HO and the compound of formula 2.50

and the compound of formula 2.51

and the compound of formula 2.52

wherein

Ri, R₂ and R₃ are each independently of the others halogen, nitro, cyano, C₁-C₄alkyl, C₂-C alkenyl, C₂-C₄alkynyl, Cι-C₄haloalkyl, C₂-C₆haloalkenyl, C₃-C₆cycloalkyl, halo- substituted C₃-C₆cycloalkyl, CrC₆alkoxyalkyl, Cι-C₆alkylthioalkyl, hydroxy, mercapto, Cι-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C C₄alkylcarbonyl, Cι-C₄alkoxycarbonyl, Cι-C₄alkylthio, C₁-C₄aikylsulfinyi, C C₄alkylsulfonyl, amino, Cι-C₄alkylamino or di(Cι-C₄- alkyl)amino; R₄ and R₅ together are a group

-C-R₆(R₇)-O-C-R₈(R₉)-C-Rιo(Rιι)-C-Rι₂(Rι₃)- (Z,),

-C-Rι₄(Rι₅)-C-Rι₆(Ri7)-O-C-R₁₈(Rι₉)-C-R₂o(R₂ι)- (Z₂), or

-C-R₂₂(R₂₃)-C-R₂ (R₂₅)-C-R₂₆(R₂₇)-O-C-R₂₈(R₂g)- (Z ), wherein R₆, R₇, R₈, R9, R10, Rn, R12, R13, Rι , R15, R16, R17, Rι₈, R19, R20, R21, R22, R23, R2₄, R₂5, R₂6, R₂7, R₂₈, and R₂₉ are each independently of the others hydrogen, halogen, CrC₄alkyl or Cι-C₄haloalkyl, it being possible for an alkylene ring, which together with the carbon atoms of the groups Zi, Z₂ or Z₃ contains from 2 to 6 carbon atoms and which may be interrupted by oxygen, to be either fused or spiro-bound to the carbon atoms of the groups Zi, Z₂ or Z₃, or that alkylene ring bridges at least one ring atom of the groups Z Z₂ or Z₃;

G is hydrogen, -C(Xι)-R₃₀, -C(X₂)-X₃-R₃ι, -C(X₄)-N(R₃₂)-R₃3, -SO₂-R₃ , an alkali metal, alkaline earth metal, sulfonium or ammonium cation or -P(X₅)(R₃₅)-R₃₆; X₁, X₂, X₃, X₄ und X₅ are each independently of the others oxygen or sulfur; and R30, R31, R3₂, R33, R3₄, R35 and R₃₆ are each independently of the others hydrogen, Cι-C₅alkyl, Cι-C₅haloalkyl, C₂-C₅alkenyl, CrC₅alkoxyalkyl, C₃-C₆cycloalkyl or phenyl, and R₃₄ is additionally C₂-C₂₀alkenyl; C₂-C₂₀alkenyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkylalkylcarbonylamino, cyano, (C₃-C₇)cycloalkyl, (C₃-C₇)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; C₂-C₂₀alkynyl; C -C₂₀alkynyl substituted by halogen, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkoxy, thioalkyl, alkylthiocarbonyl, alkylcarbonylthio, alkylsulfonyl, alkylsulfoxyl, alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyloxy, alkylsulfonylamino, alkylamino, dialkylamino, alkylcarbonylamino, dialkylcarbonylamino, alkylalkylcarbonylamino, cyano, (C₃-C₇)cycloalkyl, (C₃-C₇)heterocyclyl, trialkylsilyl, trialkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; (Cι-C₇)cycloalkyl; (C C₇)cycloalkyl substituted by halogen, haloalkyl, (Cι-C₆)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or by trialkylsilyloxy; heteroaryl; heteroaryl substituted by halogen, haloalkyl, nitro, cyano, (C C₆)alkyl, alkoxy, alkylcarbonyloxy, thioalkyl, alkylcarbonylthio, alkylamino, alkylcarbonylamino, trialkylsilyl or by trialkylsilyloxy; heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and also salts and diastereo- isomers of compounds of formula 2.52,

and the compound of formula 2.53

and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.

2. A method of controlling undesired plant growth in crops of useful plants which comprises allowing a herbicidally effective amount of a composition according to claim 1 to act on the crop plant or the area of cultivation thereof.

3. A method according to claim 2, wherein the crop plant is maize or a cereal.

4. A method according to claim 2, wherein the crop of useful plants is treated with the said composition at a rate of application corresponding to a total amount of active ingredient of from 1 to 5000 g per hectare.

5. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) an amount, effective for herbicide synergism, of the compound of formula I according to claim 1 and one or more compounds selected from the compounds of formulae 2.1 to 2.53 and the compounds prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P- ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlorotoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, trifluralin, fluthiamide, isoxaben, triallate, 2,4-DB, dichlorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin according to claim 1 and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1

and the compound of formula 3.2

and the compound of formula 3.3

thereof and salts and hydrates thereof, and the compound of formula 3.4

and the compound of formula 3.5

and the compound of formula 3.6

and the compound of formula 3.7

and the compound of formula 3.8

and of formula 3.9

CI₂CHCON(CH₂CH=CH₂)₂ (3.9),

and of formula 3.10

and of formula 3.11

and of formula 3.12

(3.12) and methyl and ethyl esters thereof and salts thereof,

and of formula 3.13

and of formula 3.14

and of formula 3.15

and of formula 3.16

and of formula 3.17

6. A method for the selective control of weeds and grasses in crops of useful plants which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with an amount, effective for herbicide synergism, of a composition according to claim 5.

7. A method according to claim 6, wherein the rate of application of herbicide is from 1 to 5000 g/ha and the rate of application of safener is from 0.001 to 0.5 kg/ha.

8. A method according to claim 6, wherein the crop of useful plants is maize or a cereal.

9. A selectively herbicidal composition that, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of the compound of formula I according to claim 1 and b) an amount, effective for herbicide antagonism, of a compound selected from the compound of formula 3.1

and the compound of formula 3.2

and the compound of formula 3.3

thereof and salts and hydrates thereof, and the compound of formula 3.4

and the compound of formula 3.5

and the compound of formula 3.6

and the compound of formula 3.7

and the compound of formula 3.8 .

and of formula 3.9

CI₂CHCON(CH₂CH=CH2)2 (3.9),

and of formula 3.10

and of formula 3.11

and of formula 3.12

(3.12), and methyl and ethyl esters thereof and salts thereof,

and of formula 3.13

and of formula 3.14

and of formula 3.15

and of formula 3.16

H₃C and of formula 3.17

10. A method for the selective control of weeds and grasses in crops of useful plants which comprises treating the useful plants, seeds or cuttings thereof, or the area of cultivation thereof, with a selective herbicidal amount of a composition according to claim 9.