WO2005077178A2

WO2005077178A2 - Herbicidal composition

Info

Publication number: WO2005077178A2
Application number: PCT/EP2005/001518
Authority: WO
Inventors: Stephen John Hole; Christoph Lüthy; Renaud Beaudegnies; Andrew Edmunds; Jürgen Schaetzer; Sebastian Wendeborn
Original assignee: Syngenta Participations Ag
Priority date: 2004-02-16
Filing date: 2005-02-15
Publication date: 2005-08-25
Also published as: WO2005077178A3

Abstract

A herbicidal composition comprising a) a compound of formula (I) wherein the substituents are as defined in claim 1, or an agronomically acceptable salt of such a compound, and b) a synergistically effective amount of one or more compounds selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula (II) and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyrafIufan-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chiortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosuifuron, diflufenican, bilanafos, ethaifluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoqual, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, 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 comprising a herbicidal active ingredient combination that is suitable for selectively controlling weeds in crops of useful plants, for example in crops of cereals. The invention relates also to a method of controlling weeds in crops of useful plants and to the use of the novel composition for that purpose.

The compounds of formula I

the substituents of which are defined hereinbelow, exhibit herbicidal action. The compounds of formula I and their preparation are known from WO 03/106448. Mixtures of cyclohexane- dione herbicides with synergists and safeners are described in WO 01/54501 .

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

There is therefore proposed in accordance with the present invention a novel synergistic composition for selectively controlling weeds which, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of a compound of formula I

wherein

L is either a direct bond, an -O-, -S-, -S(O)-, -SO₂-, -N(R_5a)-, -SO₂N(R₅b)-, -N(R_5b)SO₂-,

-C(O)N(R_5c)- or -N(R_5c)C(0)- bridge, or a C C₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain which may be mono- or poly-substituted by R₅ and/or interrupted once or twice by an

-O-, -S-, -S(O)-, -SO₂-, -N(R_5d)-, -SO₂N(R_5e)-, -N(R_5e)S0₂-_I -C(O)N(R₅,)- and/or -N(R₅,)C(O)- bridge, and when two such bridges are present those bridges are separated at least by one carbon atom, and, when the bridge L is bonded to a nitrogen atom of W, W is bonded to L by way of a carbon atom or a -N(R_5e)SO₂- or -N(R₅ )C(O)- bridge;

W is a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

which contains a ring element Ui, and may contain from one to four further ring nitrogen atoms, and/or two further ring oxygen atoms, and/or two further ring sulfur atoms and/or one or two further ring elements U_2> and the ring system U may be mono- or poly-substituted at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and two substituents R₈ together are a fused-on or spirocyclic 3- to 7-membered further ring system which may be unsaturated, partially saturated or fully saturated and may in turn be substituted by one or more groups R_8a and/or interrupted once or twice by a ring element -O-, -S-, -N(R_8b)- or -C(=O)-; and

U and U₂ are, each independently of the other(s), -C(=O)-, -C(=S)-, -C(=NR₆)-, -(N=O)-, -S(=O)- or -SO₂-;

R₃ and R₄ are, each independently of the other, CrC₃alkyl, C-ι-C₃haloalkyl, CrC₃alkoxy- C C₃alkyl, hydrogen, hydroxy, mercapto, halogen, C C₃alkoxy, C C₃haloalkoxy, C Csalkoxy-d-Caalkoxy, C C₃alkylthio, C C₃alkylsulfinyl, CrC₃alkylsulfonyl, CrC₃halo- alkylthio, CrC₃haloalkylsulfinyl, CrC₃haloaikylsulfonyl or CrC₃alkylsulfonyloxy; R₅ is halogen, CrC₃alkyl, CrC₃alkoxy, C C₃alkylthio, CrC₃alkylsulfinyl, CrC₃alkylsulfonyl, C C-saikoxy-C Caalkyl or d-Csalkoxy-C C-salkoxy; _δa, R_δ and R_5e are independently hydrogen, C C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or

Cι-C₃alkoxy-CrC₃alkyl;

R_5d is hydrogen, C C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, d-Csalkoxy-d-dalkyl, benzyl, cyano, formyl, d-C₄alkylcarbonyl, C C₄alkoxycarbonyl, d-C alkylsulfonyl or phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by R₇;

R_5c and R_5f are, each independently of the other, hydrogen or C C₃alkyl;

R₆ is d-C₆alkyl, hydroxy, d-C₆alkoxy, cyano or nitro;

R₇ is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro; each R₈ is, independently of any other, hydrogen, halogen, d-C₆alkyl, Cι-C₆haloalkyl,

C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, d-C₆alkoxy, d-C₆haloalkoxy,

C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, d-Csalkoxy-Crdaikoxy, mercapto, d-C₆alkylthio,

CrC₆alkylsulfinyl, d-Cealkylsulfonyl, d-C₆alkylsulfonyloxy, d-C₆haloalkylsulfonyloxy,

C₃-C₆alkenylthio, C₃-C₆alkynylthio, amino, Cι-C₆alkylamino, di(d-C₆alkyl)amino,

CrC₃alkoxy-Cι-C₃alkyl, formyl, d-C₄alkylcarbonyl, C C₄alkoxycarbonyl, benzyloxycarbonyl, d-C₄alkylthiocarbonyl, carboxy, cyano, carbamoyl, phenyl, benzyl, heteroaryl or hetero- cyclyl, it being possible for the phenyl, benzyl, heteroaryl and heterocyclyl groups to be mono- or poly-substituted by R_7a; each R_7a is, independently of any other, halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro; each R_8a is, independently of any other, halogen, C C₆alkyl, d-C₆haloalkyl, C₃-C₆cycloalkyl,

C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, d-C₆alkoxy, C C₆haloalkoxy, C₃-C₆alkenyloxy,

C₃-C₆alkynyloxy, mercapto, Cι-C₆alkylthio, d-C₆alkylsulfinyl, C C₆alkylsulfonyl, C C₄alkyl- carbonyl, d-C₄alkoxycarbonyl, cyano or nitro;

R_8b is hydrogen, d-C₃alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, Cι-C₃alkoxy-d-C₃alkyl or benzyl, it being possible for the phenyl group to be substituted by R_7b;

R_7b is halogen, C C₃alkyl, C-ι-C₃haloalkyl, hydroxy, d-C₃alkoxy, C C₃haloalkoxy, cyano or nitro; p is O or l ; r is 1 , 2, 3, 4, 5 or 6; with the provisos that a) R₈ and R_8a as halogen or hydrogenmercapto cannot be bonded to a nitrogen atom, b) d as -C(=O)- or -C(=S)- does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group by way of a CrC alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain L that is interrupted by -O-, -S-, -S(O)-, -SO₂-, -N(R₅d)-, -SO₂N(R_5e)- or by -N(R_5e)SO₂-, c) Ui as -C(=S)- does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group by way of a -CH=CH- or -C≡C- bridge L or by way of a d-C₄alkylene chain L that is interrupted by -O-, -S-, -S(O)-, -SO₂- or by -N(CrC₄alkyl)-, d) Ui as -C(=S)- or -C(=NR₆)- wherein R₆ is d-C₆alkyl or CrC₆alkoxy does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group directly or by way of a Cι-C₄alkylene chain L; either

Q is a group Qi

wherein

A_T is C(RnR₁₂) or NR₁₃;

A₂ is C(R_uR₁₅)_m, C(O), oxygen, NR₁₆ or S(O)_q;

A₃ is C(R₁₇R₁₈) or NR₁₉; with the proviso that A₂ is other than S(O)_q when is NRι₃ and/or A₃ is NR₁₉; - is hydroxy, O^"M⁺ wherein M⁺ is a metal cation or an ammonium cation; halogen or

S(O)_nR_9l wherein m is 1 or 2; q, n and k are, each independently of the others, 0, 1 or 2;

R_g is C C ₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂allenyl, C₃-C₁₂cycloalkyl, C₅-C₁₂cyclo- alkenyl, R ₀-CrC₁₂alkylene or R₁₀-C₂-Cι₂alkenylene, wherein the alkylene or alkenylene chain may be interrupted by -O-, -S(O)κ- and/or by -C(O)- and/or mono- to penta-substituted by R₂o; or phenyl, which may be mono- to penta-substituted by R_7c;

R_7c is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, Cι-C₃alkoxy, C C₃haloalkoxy, cyano or nitro;

R₁₀ is halogen, cyano, rhodano, hydroxy, d-C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy,

C C₆alkylthio, d-C₆alkylsulfinyl, d-C₆alkylsulfonyl, C₂-C₆alkenylthio, C₂-C₆alkynylthio,

CrC₆alkylsulfonyloxy, phenylsulfonyloxy, C C₆alkylcarbonyloxy, benzoyloxy, C C alkoxy- carbonyloxy, d-C₆alkylcarbonyl, d-C alkoxycarbonyl, benzoyl, aminocarbonyl, C C alkyl- aminocarbonyl, C₃-C₆cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl; it being possible for the phenyl-containing groups in turn to be substituted by R_7d; R_7d is halogen, d-C₃alkyl, Cι-C₃haloalkyl, hydroxy, d-C₃alkoxy, C-ι-C₃haloalkoxy, cyano or nitro;

R₂₀ is hydroxy, halogen, C C₆alkyl, C C₆aIkoxy, C_rC₆alkylthio, C C₆alkylsulfinyl, CrC₆alkylsulfonyl, cyano, carbamoyl, carboxy, d-C₄alkoxycarbonyl or phenyl; it being possible for phenyl to be substituted by R_7e;

R_7e is halogen, C C₃alkyl, d-C₃haloalkyl, hydroxy, C C₃alkoxy, d-C₃haloalkoxy, cyano or nitro;

Rn and R₁₇ are, each independently of the other, hydrogen, Cι-C₄alkyl, C₂-C₄alkenyl, C -C₄alkynyl, C C alkylthio, CrC₄alkylsulfinyl, C C₄alkylsulfonyl, C C alkoxycarbonyl, hydroxy, d-C₄aikoxy, C₃-C₄alkenyloxy, C₃-C₄alkynyloxy, hydroxy-C C₄alkyl, d-C₄alkyl- sulfonyloxy-d-C₄alkyl, halogen, cyano or nitro; or, when A₂ is C(R₁₄R₁₅)_m, Rι₇ together with R forms a direct bond or a d-C₃alkylene bridge;

R₁₂ and R₁₈ are, each independently of the other, hydrogen, d-C₄alkyl or d-C₄alkylthio, CrC₄alkylsulfinyl or d-C₄alkylsulfonyl; or R₁₂ together with Rn, and/or R₁₈ together with R_i7 form a C₂-C₅alkylene chain which may be interrupted by -O-, -C(O)-, -O- and -C(O)- or by -S(O)_r;

R₁₃ and R ₉ are, each independently of the other, hydrogen, d-C₄alkyl, CrC₄haloalkyl, C₃-C₄alkenyl, C₃-C alkynyl or C C₄alkoxy;

Rι is hydrogen, hydroxy, d-C₄alkyl, CrC₄haloalkyl, C C₃hydroxyalkyl, d-C₄alkoxy-d-C₃- alkyl, C C₄alkylthio-d-C₃alkyl, d-dalkylcarbonyloxy-d-C-salkyl, C C₄alkylsulfonyloxy- d-C₃alkyl, tosyloxy-d-C₃alkyl, di(d-C₄alkoxy)-CrC₃alkyl, C C₄alkoxycarbonyl, C₃-C₅- oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C dioxacycloalkyl, C₃-C dithiacycloalkyl, C₃-C₄oxa- thiacycloalkyl, formyl, d-C alkoxyiminomethyl, carbamoyl, Cι-C₄alkyiaminocarbonyl or di- (CrC alkyl)aminocarbonyl; or R₁ together with Rn, R₁₂, R₁3, R₁₅, Rι , Rιs or R₁₉ or, when m is 2, also together with R forms a direct bond or a d-C₄alkylene bridge; R₁₅ is hydrogen, C C₃alkyl or Cι-C₃haloalkyl;

R₁₆ is hydrogen, C C₃alkyl, d-C₃haloalkyl, d-C alkoxycarbonyl, d-C₄alkylcarbonyl or N,N- di(Cι-C₄alkyl)aminocarbonyl; or Q is a group Q₂

wherein

R₂₁ and R₂₂ are hydrogen or C C₄alkyl;

X₂ is hydroxy, O^"M⁺ wherein M⁺ is an alkali metal cation or ammonium cation; halogen, d-Cι₂alkylsulfonyloxy, d-C-^alkylthio, CrC₁₂alkylsulfinyl, d-Cι₂alkylsulfonyl, C C₁₂halo- alkylthio, d-C₁₂haloalkylsulfιnyl, CrC^haloalkylsulfonyl, d-Cealkoxy-d-Cealkylthio, d-C₆- alkoxy-d-C₆alkylsulfinyl, d-Cealkoxy-CrCealkylsulfonyl, C₃-C₁₂alkenylthio, C₃-C₁₂alkenyl- suifinyl, C₃-C₁₂alkenylsulfonyl, C₃-Cι₂alkynylthio, C₃-C₁₂alkynylsulfinyl, C₃-C₁₂alkynylsulfonyl, d-C₄alkoxycarbonyl-d-C₄alkylthio, d-C₄alkoxycarbonyl-d-C₄alkylsulfinyl, d-C alkoxy- carbonyl-CrC₄alkylsulfonyl, benzyloxy or phenylcarbonylmethoxy; it being possible for the phenyl-containing groups to be substituted by R_7f;

R_7t is halogen, C C₃alkyl, d-C₃haloalkyl, hydroxy, C C₃alkoxy, C C₃haloalkoxy, cyano or nitro; or

Q is a group Q₃

wherein

R_3i is C_rC₆alkyl, d-C₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl;

R₃₂ is hydrogen, C C₄alkoxycarbonyl, carboxy or a group S(O)_sR3₃;

R₃₃ is d-C₆alkyl or d-C₃alkylene, which may be substituted by halogen, d-C₃alkoxy,

C₂-C₃alkenyl or by C₂-C₃alkynyl; and s is 0, 1 or 2; or

Q is a group Q₄

wherein

R₄₁ is Cι-C₆alkyl, C C₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl; or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I, and b) a synergistically effective amount of one or more compounds selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, py raf I uf en-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin.

The invention also includes the salts which the compounds of formula I are 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 as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-C₁₈alkylamines, C C hydroxyalkylamines and C₂-C₄alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropyiamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexyl- amine, 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 arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropyiamine and diisopropylamine.

The alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl and the branched isomers thereof. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated, C₂-C₁₂alkyl chains having one or more double or triple bonds also being included. Alkenyl is, for example, vinyl, allyl, isobuten-3-yl, CH₂=CH-CH₂-CH=CH₂-, CH₂=CH-CH₂-CH₂-CH=CH₂- or CH₃-CH=CH-CH₂-CH=CH-. A preferred alkynyl is, for example, propargyl, and CH₂=C=CH₂- is a preferred ailenyl.

An alkylene chain may be substituted by one or more d-C₃alkyl groups, especially by methyl groups; such alkylene chains and alkylene groups are preferably unsubstituted. The same applies to all groups containing C₃-C₆cycloalkyl, C₃-C₅oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C₄dioxacycloalkyl, C₃-C₄dithiacycloalkyl or C₃-C oxaathiacycloalkyl.

An alkylene chain uninterrupted or interrupted by oxygen, S(O)_k, -S(O)ι, -NR - or by carbonyl and especially a d-C alkylene chain L which may be unsubstituted or substituted one or more times (up to five times) by R₅ and/or uninterrupted or interrupted once or twice by -O-, -S(O)_r> -N(R_5d)-, -SO₂N(R_5e)-, -N(R_5e)SO₂-, -C(O)N(R_5f)- or by -N(R_5f)C(O)-, which groups are separated at least by one carbon atom, and, when the bridge L is bonded to a nitrogen atom of W, W is bonded to L by way of a carbon atom or a -N(R_5e)SO₂- or -N(R_5f)C(O)- bridge; is to be understood as being, for example, a chain -CH₂-, -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH(CH₃)-, -CH₂CH(CH₃)-, -CH₂CH(CH₃)CH₂-, -CH₂CH(CI)CH₂-, -CH₂CH(OCH₃)CH₂-, -CH₂O-, -OCH₂-, -CH₂OCH₂-, -OCH₂CH₂-, -OCH₂CH₂CH₂-, -CH₂OCH₂CH₂-, -CH₂OCH(CH₃)CH₂-, -SCH₂-, -SCH CH₂-, -SCH₂CH₂CH₂-, -CH₂S-, -CH₂SCH₂-, -CH₂S(O)CH₂-, -CH₂SO₂CH₂-, -CH₂SCH₂CH₂-, -CH₂S(O)CH₂CH₂-, -CH₂SO₂CH₂CH₂-, -CH₂SO₂NH-, -CH₂N(CH₃)SO₂CH₂CH₂-, -N(SO₂Me)CH₂CH₂-, -CH₂C(O)NH- or -CH₂NHC(O)CH₂-. The definition R₁₀-Cι-C₁₂alkylene which may be interrupted by oxygen or by -S(O)_n- denotes, for example, CH₃OCH₂CH₂O-, phenoxy, phenoxymethyl, benzyloxy, benzylthio or benzyloxymethyl.

A C₂-C₄alkenylene chain which may be uninterrupted or interrupted by oxygen is accordingly to be understood as being, for example, -CH=CH-CH₂-, -CH=CH-CH₂CH₂- or -CH=CHCH₂OCH₂-, and a C₂-C₄alkynylene chain which may be uninterrupted or interrupted by oxygen is to be understood as being, for example, -C≡C-, C≡CCH₂-, -C≡CCH₂O-, -C≡CCH₂OCH₂- or -OC≡CCH₂-.

An alkylene chain which may be mono- or poly-substituted by R₅ in d-C₄alkylene or by R₂₀ in R₁₀-Cι-Cι₂alkylene may be substituted, for example, up to five times. Two such substituents as C C₃alkyl may together also form a 3- to 8-membered ring, the groups in question being located at the same carbon atom or at adjacent atoms.

W as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

is to be understood as being especially a heterocyclic ring system U which contains a ring element U-i and which may contain from one to four further ring nitrogen atoms, and/or one or two further ring oxygen atoms, and/or one or two further ring sulfur atoms and/or one or two further ring elements U₂, and which may be substituted one or more times (e.g. up to six times) at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and in which two radicals R₈ together may be a fused-on or spirocyclic 3- to 7- membered further ring system, which may likewise be unsaturated, partially saturated or fully saturated and may itself be substituted by one or more groups R_8a; and wherein Ui and U₂ are, each independently of the other, -C(=O)-, -C(=S)-, -C(=NR₆)-, -(N=O)-, -S(=O)- or -SO₂-. Such ring systems U are, for example,

wherein R₅₄, R₅₆, R₅₈, R₅₉, R₆₂, Res, Ree, Rβ7, Res and R₆₉ as sub-groups of selected substituents R₈ have the definitions and preferred meanings indicated hereinbelow. W as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U is preferably a heterocyclic group U₀

wherein Ri together with R₂, by way of the nitrogen atom and the ring element U_L, forms the corresponding ring system U, which may additionally contain up to 3 nitrogen atoms, a further oxygen atom, a further sulfur atom or a further group U₂ and which may additionally be substituted one or more times (for example up to six times) at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and in which two substituents R₈ together may be a fused-on or spirocyclic 3- to 7-membered further ring system, which may likewise be unsaturated, partially saturated or fully saturated and may itself be substituted by one or more groups R_8a. W is especially a heterocycle selected from the groups

U, 009, Ul .010, Ui .011 I U1.012,

Ui 028,

wherein R₅ , R₅₃, R₅₆, R₆₅ are, each independently of the others, hydrogen, halogen, d-C₆- alkyl, d-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C₁-C₃alkoxy-C₁-C₃alkyl, d-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C C₆alkylthio, d-C₆alkylsulfinyl, CrCealkyl- sulfonyl, C₃-C₆alkenylthio or C₃-C₆alkynylthio; R₅₂ is hydrogen, C C₆alkyl, d-C₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, C C₆alkoxy, amino, or phenyl which may in turn be substituted by R₇₀; R₅₄, R₅₅, R₆o are hydrogen, d-C₆alkyl, d-C₆haloalkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or C₃-C₆cycloalkyl; R5₇, Re3, Ree, Rβ7, Res, Reg are C C₆alkyl, or phenyl which may in turn be substituted by R₇₀; R₆₄ is C C₆alkyl, CrC₆haloalkyl, C₃-C₆cycloalkyl, C₃-C₆- alkenyl, C₃-C₆alkynyl, or phenyl which may in turn be substituted by R₇₀; R₅₈, Rεi are hydrogen, halogen, d-C₆alkyl or C C₆haloalkyl; R₅₉ is Cι-C₆alkyl, d-C₆haloalkyl, C C₃- alkoxy-C Csalkyl, C₃-C₆alkenyl or C₃-C₆alkynyl; R₆₂ is hydrogen, d-C₆alkyl, C C alkoxy- carbonyl or d-C alkylthiocarbonyl; or R₅₁ together with R₅₂, or R₅₄ together with an adjacent group R₅₆, or R₅₈ together with an adjacent group R₅₉₎ or R₆₀ together with an adjacent group R₆₁, or, when r is 2, two adjacent groups R₅₆ or two adjacent groups R₆ι together may form a saturated or unsaturated CrC₅alkylene or C₃-C alkenylene bridge which may in turn be substituted by a group R₇₀ or interrupted by oxygen, sulfur or by nitrogen; each R₇₀ independently is halogen, C C₃alkyl, d-C₃haloalkyl, hydroxy, C C₃alkoxy, d-C₃haloalkoxy, cyano or nitro; X is oxygen, sulfur or NR₆; X₃, X₄ and X₅ are oxygen or sulfur; X₆ and X₇ are oxygen or S, S(O), SO₂; and X₈ is CH₂, oxygen, S, S(O), SO₂ or NR₇ι, wherein R₇₁ is hydrogen or d-C₆alkyl.

Two substituents R₈ as hydroxy may be a further carbonyl group when they are located at the same carbon atom, and two substituents R₈ that together form a further 3- to 7- membered ring system may be located at the same carbon atom to form a spiro ring or at two adjacent carbon and/or nitrogen atoms to form a fused ring system, such as, for example, in the case of the groups

The provisos that Id as either -C(=O)- or -C(=S)- or -C(=NR₅ )- does not form a tautomeric form with a substituent R₈ as hydrogen are to be understood as meaning especially that an enol form is not formed under physiological conditions in a pH range of from about 2 to about 11. Accordingly, the present invention likewise relates, for example, to compounds of formulae

Ui 009a, Ui Q1₂a and Ui 028a-

Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. The same is true of halogen in conjunction with other meanings, such as haloalkyl, haloalkoxy or halophenyl.

Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoro- methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichioromethyl, 2,2,2- trifluoroethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-fluoroprop-2-yl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, pentafluoroethyl, heptafluoro-n-propyl, perfluoro-n-hexyl. Preferred haloalkyl groups in the definitions R to R_x, and particularly the group R₃, are fluoromethyl, difluoromethyl, difluorochloromethyl, trifluoromethyl and pentafluoroethyl.

As haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine or iodine, and especially fluorine or chlorine, for example 1 -chlorovinyl, 2-chlorovinyl, 2,2-difluoro-vinyl, 2,2-difluoro-prop-1 -en-2- yl, 2,2-dichloro-vinyl, 3-fluoroprop-1 -enyl, chloroprop-1 -en-1 -yl, 3-bromoprop-1 -en-1-yl, 3- iodoprop-1-en-1-yl, 2,3,3-trifluoroprop-2-en-1-yl, 2,3,3-trichloroprop-2-en-1-yl and 4,4,4- trifluoro-but-2-en-1 -yl.

As haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly- substituted by halogen, halogen being bromine, iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1 -yl.

A C₃-C₆cycloalkyl group may likewise be mono- or poly-substituted by halogen, for example 2,2-dichlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2,3,3-tetrafIuorocyclobutyl or 2,2-difluoro- 3,3-dichlorocyclobutyl.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert- butoxy or a pentyloxy or hexyloxy isomer; preferably methoxy or ethoxy.

Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms, e.g. fluoro- methoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 1 -f luoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably fluoromethoxy, difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms.

Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutyl- thio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutyl- sulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or a butylamine isomer. Dialkylamino is, for example, dimethylamino, methylethylamino, diethyl- amino, n-propylmethylamino, dibutylamino or diisopropylamino. Alkylamino groups having a chain length of from 1 to 4 carbon atoms are preferred.

Alkoxyalkyl groups preferably have from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkoxy-alkoxyalkyl groups preferably have from 3 to 8 carbon atoms, e.g. methoxymethoxymethyl, methoxyethoxymethyl, ethoxymethoxymethyl, ethoxyethoxy methyl. Di(Cι-C₄alkoxy)-CrC alkyl is to be understood as being, for example, dimethoxymethyl or diethoxymethyl.

Alkylthioalkyl groups preferably have from 2 to 6 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.

Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxy- carbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, iso- butoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl, ethoxycarbonyl or tert-butoxycarbonyl.

Phenyl, including phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl or tosyl, can be in mono- or poly-substituted form. The substituents can in that case be as desired, preferably with a substituent having a meaning of R₇ in the ortho-, meta- and/or para-position. Heteroaryl is to be understood as being a 5- or 6-membered group containing both nitrogen and oxygen and/or sulfur, for example furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, triazinyl, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, 4,5-dihydro-isoxazole, 2-pyranyl, 1 ,3-dioxol-2-yl, oxiranyl, 3- oxetanyl, tetrahydrofuranyl, tetrahydropyranyl or one of the groups Ui defined above.

Heterocyclyl is to be understood as being a ring system containing, in addition to carbon atoms, at least one hetero atom, such as nitrogen, oxygen and/or sulfur. It may be saturated or unsaturated. Heterocyclyl ring systems in the context of the present invention may also be substituted. Suitable substituents are, for example, d-C₄alkyl, Cι-C₄haloalkyl, C C₄alkoxy, cyano, nitro, d-C₄alkylsulfonyl, d-C₄alkylsulfinyl, C C₄alkylthio and C₃-C₆cycloalkyl.

Depending upon the preparation process, the compounds of formula I may be obtained in various tautomeric forms, such as, for example, in Form A shown below or in Form B or in Form C, preference being given to Form A, as shown by way of example for compounds of formula IA wherein Q is a group Qi and the group -L-W is in the 2-position.

IA, Form A IA, Form B IA, Form C

When -_\ is hydroxy, the structure of formula I can also be represented by the tautomeric Form D

IA, Form D (X₁ = hydroxy) as shown likewise by way of the example of compounds of formula IA wherein Q is a group Qi and the group -L-W is in the 2-position. Compounds of formula I wherein Q is a group Q₂ or a group Q₄ may accordingly be present in the tautomeric forms A, B, C or D. When a C=N or C=C double bond is present in compounds of formula I, the compounds of formula I, when asymmetric, may be in the E form or the Z form. When a further asymmetric centre is present, for example an asymmetric carbon atom, chiral R or S forms may occur. The present invention therefore also encompasses all such stereoisomeric and tautomeric forms of the compound of formula I.

It is extremely surprising that the combination of the active ingredient of formula I with one or more active ingredients selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyi, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclof op-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin exceeds the additive effect 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 formula I and pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 and, 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 unusable from the agronomic standpoint. The result is a considerable 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 enables 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 and also against undesirable volunteer crops. The composition according to the invention is suitable for all methods of application conventionally used in agriculture, e.g. 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, and also for non-selective weed control.

Crops are to be understood as including those that have been made tolerant to herbicides or classes of herbicides (e.g. HPPD-inhibitors, ALS-inhibitors, EPSPS-inhibitors (5-enol- pyruvyl-shikimate-3-phosphate synthase inhibitors) and GS-inhibitors (glutamine synthetase inhibitors) by means of conventional breeding or genetic engineering methods. An example of a crop that has been made tolerant by conventional breeding methods (mutagenesis) to, for example, imidazolinones such as imazamox is Clearfield® summer rape (canola). Examples of crops made tolerant to herbicides or classes of herbicides by genetic engineering methods are maize varieties resistant to, for example, glyphosate or glufosinate or L-glufosinate, which are commercially available under the trade names RoundupReady® and LibertyLink®.

Crops are also to be understood as including those that have been made resistant to harmful insects by means of genetic engineering methods. Such crops have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria-colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins; plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood by δ-endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). An example of a truncated toxin is a truncated CrylA(b), which is expressed in Bt11 maize of Syngenta Seeds SAS, as described hereinbelow. In the case of modified toxins, one or more amino acids of the naturally occurring toxin is/are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D- recognition sequence is inserted into a CrylllA toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants provides the plants with tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

The following harmful insects from different taxonomic groups are especially common in maize crops:

Ostrinia nubilalis, European corn borer

Agrotis ipsilon, black cutworm

Helicoverpa zea, corn earworm

Spodoptera frugiperda, fall armyworm

Diatraea grandiosella, southwestern corn borer

Elasmopalpus lignosellus, lesser cornstalk borer

Diatraea saccharalis, sugarcane borer

Diabrotica virgifera virgifera, western corn rootworm

Diabrotica longicornis barberi, northern corn rootworm

Diabrotica undecimpunctata howardi, southern corn rootworm

Melanotυs spp., wireworms

Cyclocephala borealis, northern masked chafer (white grub)

Cyclocephala immaculata, southern masked chafer (white grub)

Popillia japonica, Japanese beetle

Chaetocnema pulicaria, corn flea beetle

Sphenophorus maidis, maize billbug

Rhopalosiphum maidis, corn leaf aphid

Anuraphis maidiradicis, corn root aphid Blissυs Iθucopterus leucopterus, chinch bug Mθlanoplus femurrubrum, red-legged grasshopper Mθlanoplus sanguinipes, migratory grasshopper Hylemya platura, seedcom maggot Agromyza parvicornis, corn blotch leafminer Anaphothrips obscurus, grass thrips Solenopsis milesta, thief ant Tetranychus urticae, two-spotted spider mite

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CryΙA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); NatureGard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European com borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thu ngiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, including the European corn borer.

Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch). The compositions according to the invention are also excellently suitable for use in fungus- resistant transgenic crop plants. In the context of the present invention, fungus-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).

Of the compounds of formula I, the formulae IA, IB, IC, ID, IE, IF, IG and IH are preferred for the composition according to the invention.

IA IB IC

ID

Special preference is given to the compounds of formula IA.

Of the compounds of formula I, special preference is given, for the composition according to the invention, to those wherein W, as a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

is a group bonded to L by way of the nitrogen atom adjacent to the ring element U-i and is accordingly a cyclic group U₀ mono- or poly-substituted by R₈

wherein Ri together with R₂, by way of the nitrogen atom and the group Ui, forms the corresponding ring system U and wherein U-i, R₈ and r are as defined above.

Of the compounds of formula I and especially of the compounds of formula IA, special preference is given in turn to those groups wherein: a) Q is a group Qi, Ai is CRπRι₂ and Rn is hydrogen, methyl, ethyl, propargyl, methoxy- carbonyl, ethoxycarbonyl, methylthio, methylsulfinyl or methylsulfonyl and R₁₂ is hydrogen or methyl, or Rn together with R₁₂ forms an ethylene bridge -(CH₂)₂-; b) Q is a group Qi and A₂ is CRι₄Rι₅ or an ethylene bridge -(CH₂)₂-, and R₁₄ is hydrogen, methyl or trifluoromethyl and R₁₅ is hydrogen or methyl, or R₁₄ together with Rn, or Rι₄ together with Rι₇ forms a direct bond or a methylene bridge; c) Q is a group Qi and A₂ is C(O) and Rn, Rι₂, Rι₇ and Rι₈ are each methyl; d) Q is a group Qi and A₂ is oxygen and Rn, Rι₂, R₁₇ and R ₈ are each hydrogen or methyl; e) Q is a group Q^ and A₃ is CR₁₇R₁₈ and R₁₇ and R₁₈ are hydrogen or methyl, or Rι₇ together with R forms a methylene or ethylene bridge; f) Q is a group Qi and X-i is hydroxy; g) Q is a group Q₂ and R₂₁ is methyl or ethyl and R₂₂ is hydrogen or methyl; h) Q is a group Q₂ and X₂ is hydroxy; i) Q is a group Q₃ or Q₄ and R₃₂ is hydrogen, methylthio or methylsulfinyl, and R₃ι and R₄₁ are cyclopropyl; j) p is 0; k) R₄ is hydrogen, methyl, chlorine or trifluoromethyl, especially hydrogen; I) R₃ is Cι-C₃haloaikyl, especially difluoromethyl, chlorodifluoromethyl or trifluoromethyl; m) L is either a direct bond or an unsubstituted d-C₃alkylene group or a C C₃alkylene group uninterrupted or interrupted by oxygen, such as especially a methylene group

-CH₂- or an ethylenemethoxymethylene group -CH₂OCH₂CH₂-; n) Ri and R₂ in the group

form a 4- to 6-membered, saturated or partially saturated ring system which may additionally be substituted from one to three times by

-N(R_8b)-, once by oxygen, once by sulfur, sulfinyl or sulfonyl and/or once by a further carbonyl group; 0) UT is preferably a -C(=O)- group, a -C(=S)- group, a -C(=NR₆)- group or a -SO₂- group;

p) the group

(U_L∞_I);

q) the group

r) the group -N(R₂)U₁R₁ is

(Ui 003)!

s) the group -N(R₂)U R₁ is

t) the group -N(R₂)U₁R₁ is

(Ui 005);

u) the group -N(R₂)U₁R₁ is

v) the group

(U₁₀₀₇); w) the group -N(R₂)U R₁ is a group selected from

(U1011);

x) t

he group -N(R₂)U₁R₁ is Ui ₀₁₂ wherein X₆ is oxygen or sulfur; y) the group -N(R₂)UιR₁ is

(U-, ₀₁₃) wherein X₇ is oxygen or sulfur;

z) the group -N(R₂)U R₁ is

_OT4) wherein X is oxygen or sulfur and X_ε is -CH-;

aa) the group -N(R₂)U₁R₁ is

(Ui 02₂);

bb) the group -N(R₂)U₁R₁ is

(U₁₀₂₅);

cc) the group -N(R₂)U_!Rι is

(U₁₀₂s);

dd) the group -N(R₂)U₁R₁ is ₀₂₉; or

ee) the group -N(R₂)UιR is

(U₁₀3o). Special preference is given to the compounds of formula IA

wherein Q, L, Ui, R_L R₂, R₈ and r are as defined above and R₃ is difluoromethyl, chlorodifluoromethyl or trifluoromethyl, R₄ is hydrogen and p is 0.

Compounds of formula I which are especially preferred for the composition according to the invention are indicated in the Tables hereinbelow:

/^R 1

N^ R In the following Tables, the linkage site of the individual structures of the group ² to the substituent L is the nitrogen atom located at the same geometric position, as indicated in each case.

CH,

For example, the linkage site of the group °T ^N in the case of compound A 1.001

is the position indicated by an arrow:

is the free valency at the nitrogen atom (arrow): u~~

/

The free bonds in these structures are terminal CH₃ groups,

such as, for example, in the case of the structure ~ which can also be represented as follows:

Table A1 : Compounds of formula lAa-L

A1.004 CF₃ CH₂OCH₂CH₂

A1.005 CF₂CI CH OCH₂CH

A1.006 CHF₂ CH₂OCH₂CH₂ H₃

Vy

A1.008 CF₂CI CH₂ / CH,

A1.010 CF₃ CH₂OCH₂CH₂

A1.011 CF₂CI CH₂OCH₂CH₂

A1.012 CHF₂ CH₂OCH₂CH₂

A1.013 CF₃ CH_{2 0} F*

N CH,

A1.016 CF₃ CH₂OCH₂CH_{2 0} f^H*

A1.017 CF₂CI CH₂OCH₂CH_{2 0} F^H* A1.018 CHF₂ CH₂OCH₂CH_{2 0} »

A1.022 CF₃ CH₂OCH₂CH₂ V ^N-

A1.023 CF₂CI CH₂OCH₂CH₂ Vv /

A1.024 CHF₂ CH₂OCH₂CH_{2 0} /

I °

A1.025 CF₃ CH₂ ~~

Vv _'

A1.026 CF₂CI CH₂ /-^"

Vv >

A1.027 CHF₂ CH₂ /—

A1.028 CF₃ CH₂OCH₂CH₂ /—

A1.029 CF₂Cl CH₂OCH₂CH₂

A1.030 CHF₂ CH₂OCH₂CH₂ f

A1.035 CF₂CI CH₂OCH₂CH₂

A1.037 CF₃ CH₂ / ^ o

N

A1.039 CHF₂ CH₂ o..

-o

A1.040 CF₃ CH₂OCH₂CH_{2 0} /

N. ?^~ O

A1.041 CF₂CI CH₂OCH₂CH_{2 0} /

I />— o

A1.042 CHF₂ CH₂OCH₂CH_{2 0} /

^N-N

Comp. R₃ L ^•R i no.

A1.047 CF₂CI CH₂OCH₂CH₂

A1.048 CHF₂ CH₂OCH₂CH₂

V T \- o f

A1.053 CF₂CI CH₂OCH₂CH₂

Comp. R3 ,R no.

A1.059 CF≥CI CH₂OCH₂CH₂

A1.065 CF₂CI CH₂OCH₂CH₂

p

A1.067 CF₃ CH₂

N

Comp. no. N,

^R;

A1.071 CF₂CI CH₂OCH₂CH₂

A1.074 CF₂CI CH₂

I ,.N

A1.075 CHF₂ CH_{2 0} /

T ,N

A1.076 CF₃ CH₂OCH₂CH_{2 0} /

Y\

A1.077 CF₂CI CH₂OCH₂CH_{2 0} /

I ,N

A1.078 CHF₂ CH₂OCH₂CH_{2 0} /

A1.079 CF₃ CH₂ ^s _\

A1.080 CF₂CI CH₂ °v^s _\

A1.081 CHF₂ CH₂ °v^s _\

A1.082 CF₃ CH₂OCH₂CH₂ °γs,

A1.083 CF₂CI CH₂OCH₂CH₂ \

A1.084 CHF₂ CH₂OCH₂CH₂

A1.085 CF₃ CH₂ O^ ^s o_\ O

Y s"°

A1.086 CF₂CI CH₂ ^s _x u,₀

A1.088 CF₃ CH₂OCH₂CH₂ Q O *°

A1.089 CF₂CI CH₂OCH₂CH₂ V-NV" \-

A1.090 CHF₂ CH₂OCH₂CH₂ O τ. ς Or°

A1.091 CF₃ CH₂ T „ o

A1.092 CF₂CI CH₂ vy

A1.093 CHF₂ CH₂ ^'TV

A1.094 CF₃ CH₂OCH₂CH₂ °γVs,

A1.095 CF₂CI CH₂OCH₂CH₂

A1.096 CHF₂ CH₂OCH₂CH₂ °γ X/

A1.098 CF₂CI CH₂ ° °<

X

A1.099 CHF₂ CH₂ °T°V-

A1.100 CF₃ CH₂OCH₂CH₂

A1.101 CF₂CI CH₂OCH₂CH₂ °

^N-N

A1 .102 CHF₂ CH₂OCH₂CH₂ °γo Comp. R_a -R , no.

A1.105 CHF₂ CH₂

^N-N F

A1.106 CF₃ CH₂OCH₂CH₂ O_^

TV F

A1.107 CF₂CI CH₂OCH₂CH₂ °yo

^N-N F

A1.108 CHF₂ CH₂OCH₂CH₂

A1.109 CF₃ CH₂

A1.110 CF₂CI CH₂ v>

A1.111 CHF₂ CH₂ °τ

A1.113 CF₂CI CH₂OCH₂CH₂

A1.114 CHF₂ CH₂OCH₂CH₂ °n

A1.118 CF₃ CH₂OCH₂CH₂

A1.119 CF₂CI CH₂OCH₂CH₂ °*

' " -ci

A1.120 CHF₂ CH₂OCH₂CH₂

^\_, ci

N^

A1.122 CF₂CI CH₂

N-_S'

A1.125 CF₂CI CH₂OCH₂CH₂

A1.126 CHF₂ CH₂OCH₂CH₂ " x

A1.130 CF₃ CH₂OCH₂CH₂ ⁰γ

\ . O

A1.131 CF₂CI CH₂OCH₂CH₂ °γ

\ . O

A1.132 CHF₂ CH₂OCH₂CH₂ ° ^

\ - o

A1.133 CF₃ CH₂

<r° Comp. R3 L no. R .

A1.137 CF₂CI CH₂OCH₂CH₂ T ^ β -o

A1.138 CHF₂ CH₂OCH₂CH₂

A1.140 CF₂CI CH₂ °γ

A1.142 CF₃ CH₂OCH₂CH₂ ^u Λ

A1.143 CF₂CI CH₂OCH₂CH₂ ° Λ

A1.144 CHF₂ CH₂OCH₂CH₂

N~θ'

A1.147 CHF₂ CH₂ °n

A1.149 CF₂CI CH₂OCH₂CH₂ °γ\

A1.154 CF₃ CH₂OCH₂CH₂

A1.155 CF₂CI CH₂OCH₂CH₂

A1.156 CHF₂ CH₂OCH CH

A1.157 CF₃ CH₂ CHF₂

Vv

A1.160 CF₃ CH₂OCH₂CH₂

A1.161 CF₂CI CH₂OCH₂CH₂

A1.162 CHF₂ CH OCH₂CH₂ CHF₂

Vv

Comp. R₃ L u^^Rι

I¹ no. R₂

A1.164 CF₂CI CH₂ f\

A1.165 CHF₂ CH₂ %

A1.167 CF₂CI CH₂OCH₂CH₂ f

-^ _^

T>

A1.168 CHF₂ CH₂OCH₂CH₂ x^

TJ

A1.173 CF₂CI CH₂OCH₂CH₂

A1.175 CF₃ CH₂ vC o

A1.178 CF₃ CH₂OCH₂CH₂

V „ v> o

A1.179 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L R, no.

A1.185 CF₂CI CH₂OCH₂CH₂

A1.187 CF₃ CH₂

T ~ CH₃ H^ ³

A1.188 CF₂CI CH₂ °v T° />— CH₃

A1.189 CHF₂ CH₂

T<\h— CH,

A1.190 CF₃ CH₂OCH₂CH₂ T -CH₃

A1.191 CF₂CI CH₂OCH₂CH₂

T - CH₃

A1.192 CHF₂ CH₂OCH₂CH₂ °v T-°>— CH₃

A1.193 CF₃ CH₂ v>

A1.195 CHF₂ CH₂ v>

A1.196 CF₃ CH₂OCHCH₂ V>

A1.197 CF₂CI CH₂OCH₂CH₂ V>

A1.198 CHF₂ CH₂OCH₂CH₂ v> Comp. R₃ L ../^R i

T¹ no. N_

A1.202 CF₃ CH_{2 s} F^H*

V>

A1.203 CF₂CI CH_{2 s} ?^H°

V>

A1.204 CHF₂ CH_{2 s} f"³

V>

A1.205 CF₃ CH₂OCH₂CH_{2 s} V"^N P_\ ^H°

A1.206 CF₂CI CH₂OCH₂CH_{2 s} ?^H° V"

A1.207 CHF₂ CH₂OCH₂CH_{2 s} f^H°

"^■ V

Comp. R₃ 'R , no. R ₂

A1.214 CF₂CI CH₂ o. i CH,

A1.215 CHF₂ CH₂ PH,

A1.216 CF₃ CH₂OCH₂CH₂

A1.217 CF₂CI CH₂OCH₂CH₂

A1.218 CHF₂ CH₂OCH₂CH₂

A1.222 CF₃ CH₂ o.

N

A1.224 CF₃ CH₂ O. N Comp. R3 L _y^^Rι no. "V

A1.227 CCIF₂ CH₂ o.

N

A1.231 CHF₂ CH₂

A1.232 CHF₂ CH₂ t-

N^'

A1.234 CHF₂ CH₂

^°Ό

A1.235 CF₃ CH₂

I^N

A1.237 CF₃ CH₂

13^N CK

A1.238 CHF₂ CH₂ ° ^ _/=_\

A1.241 CHF₂ CH₂ τ>-o

A1.243 CF₃ CH₂ CH₃

A1.245 CF₃ CH₂ Vv

Table A2: Compounds of formula lAa?:

Comp. R₃ /R i no.

A2.008 CF₃ CH₂ V Iv>— CH₃

A2.010 CF₃ CH₂ V '° N^N CH₃

A2.014 CF₃ CH₂ CH,

o

A2.015 CF₃ CH₂ CH,

V>

A2.017 CF_; CH,

Table A3: Compounds of formula IAa₃:

Comp. R₃ ^•R , no.

Comp. R3 L /R, Y¹ no.

A3.008 CF₃ CH₂ V 1 -CH₃

A3.009 CF₃ CH₂ V 1 -CH₃

A3.010 CF₃ CH₂ 1 -s=o

^N-N CH₃

A3.011 CF₃ CH₂

1 -o

A3.014 CF₃ CH₂

V>

Comp. R₃ ^•R i no.

A3.019 CF₃ CH₂ T>

Table A4: Compounds of formula IAa₄:

Comp. R₃ -R ι no.

CH CHF,

A4.007 CF₃ /

T CH,

A4.008 CF₃ CH₂ CH, .'/

Comp. R₃ vr no.

A4.017 CF₃ CH₂ CH₃

A4.019 CF₃ CH₂ ^0< \

A4.020 CF₃ CH₂ °^

N— I

Table A5: Compounds of formula IAa_R:

Comp. R₃ L /^R 1 no.

A5.001 CF₃ CH₂ V 1V KcH₃

A5.008 CF₃ CH₂ V 1v h— CH₃

A5.009 CF₃ CH₂ V 1v h— CH₃

A5.010 CF₃ CH₂ V '° N^{^} CH₃

A5.017 CF₃ CH₂

A5.020 CF₃ CH₂ O

N— I

Table A6: Compounds of formula IAa_£

A6.004 CF₃ CH₂OCH₂CH₂

A6.005 CF₂CI CH₂OCH₂CH₂ pH₃

V--^F _F

A6.006 CHF₂ CH₂OCH₂CH₂ pn₃ i

A6.008 CF₂CI CH₂ H, vy, CH,

A6.009 CHF₂ CH₂ PH, vy CH,

A6.010 CF₃ CH₂OCH₂CH₂ H₃

C.H,

A6.011 CF₂CI CH₂OCH₂CH₂ H₃ v CH,

KLv ^■ / Comp. R₃ L no. ^R'

V

A6.012 CHF₂ CH₂OCH₂CH₂

A6.016 CF₃ CH₂OCH₂CH₂

A6.017 CF₂CI CH₂OCH₂CH₂

A6.018 CHF₂ CH₂OCH₂CH₂

A6.019 CF₃ CH₂ v ⁷

A6.021 CHF₂ CH₂

^N~N

A6.022 CF₃ CH₂OCH₂CH₂ V⁷

A6.023 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L _V no.

A6.027 CHF₂ CH₂

V 1 \ Ko /

A6.029 CF₂CI CH₂OCH₂CH₂

A6.035 CF₂CI CH₂OCH₂CH

„ V\ ? /

A6.036 CHF₂ CH₂OCH₂CH₂ o Vv y /

A6.037 CF₃ CH₂ v v

A6.038 CF₂CI ^CH2 KL( /K' d

A6.040 CF₃ CH₂OCH₂CH_{2 o} N /

TV. '/ O

A6.041 CF₂CI CH₂OCH₂CH₂

A6.042 CHF₂ CH₂OCH₂CH_{2 0} I _r τv_°

A6.044 CF₂CI CH_{2 0} r

V ^I \ K- r

A6.047 CF₂CI CH₂OCH₂CH₂

A6.048 CHF₂ CH₂OCH₂CH₂ r

V T NL \ '/ Ko f

Comp. R₃ L 'R , no.

A6.053 CF₂CI CH₂OCH₂CH₂ y

TK

A6.056 CF₂CI CH₂ Vv

0

A6.057 CHF₂ CH₂ Vv

0 y s

A6.058 CF₃ CH₂OCH₂CH₂ Vv

0

A6.059 CF₂CI CH₂OCH₂CH₂ Vv

<Ks o

A6.060 CHF₂ CH₂OCH₂CH₂

T' no.

A6.062 CF₂CI CH₂

A6.065 CF₂CI CH₂OCH₂CH

A6.071 CF₂CI CH₂OCH₂CH₂

A6.072 CHF₂ CH₂OCH₂CH₂

A6.073 CF₃ CH₂ v

A6.074 CF₂CI CH₂

^J<^ ^ Comp. R₃ L /^R 1 no. V

A6.075 CHF₂ CH₂ °y

A6.076 CF₃ CH₂OCH CH₂ °V I .N

A6.077 CF₂CI CH₂OCH₂CH₂

A6.078 CHF₂ CH₂OCH₂CH

I ,N

A6.080 CF₂CI CH₂ Vv

A6.081 CHF₂ CH₂ vv

A6.082 CF₃ CH₂OCH₂CH₂

(P3) vv

A6.083 CF₂CI CH₂OCH₂CH₂ V/K-

A6.084 CHF₂ CH₂OCH₂CH₂ °τv

A6.086 CF₂CI CH₂ O. ς O s÷o

A6.087 CHF₂ CH₂ O. v 0 0*°

A6.088 CF₃ CH₂OCH₂CH₂ 0. q O

A6.089 CF₂CI CH₂OCH₂CH₂

A6.090 CHF₂ CH₂OCH₂CH₂

Comp. R₃ L no. v^'R* v,

A6.094 CF₃ CH₂OCH CH₂ V ^N-VN \

A6.095 CF₂CI CH₂OCH CH₂

A6.096 CHF₂ CH₂OCH₂CH₂

A6.097 CF₃ CH₂ vv

A6.098 CF₂CI CH₂ vv

A6.099 CHF₂ CH₂ vv

A6.100 CF₃ CH₂OCH₂CH₂ vv

A6.101 CF₂CI CH₂OCH₂CH

^N~N

A6.102 CHF₂ CH₂OCH₂CH₂ 1 — —

A6.103 CF₃ CH₂

^{N^}N F

A6.105 CHF₂ CH₂

^N~"N F

A6.106 CF₃ CH₂OCH₂CH ^°T ^N>^{^}N K F

A6.107 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L no. v-^R'

V

A6.110 CF₂CI CH₂ °V

A6.113 CF₂CI CH₂OCH₂CH₂

A6.114 CHF₂ CH₂OCH₂CH₂ °V

A6.115 CF₃ CH₂ °y _*

A6.116 CF₂CI CH₂ °vv«

A6.117 CHF₂ CH₂ Vv

A6.119 CF₂CI CH₂OCH₂CH₂ Vy_α

A6.120 CHF₂ CH₂OCH₂CH₂ K

A6.121 CF₃ CH₂

A6.122 CF₂CI CH₂ °κ ^N-s

A6.123 CHF₂ CH₂ ^°K

Comp. R₃ L /^R l no. K

A6.125 CF₂CI CH₂OCH₂CH₂

A6.127 CF₃ CH₂ °V

\ - o

A6.129 CHF₂ CH₂ °

N-s \* _

0

A6.131 CF₂CI CH₂OCH₂CH₂

^N-s⁺ o

A6.132 CHF₂ CH₂OCH₂CH₂

A6.137 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L /^Rl no. V

A6.140 CF₂CI CH₂ 0.

^6

A6.141 CHF₂ CH₂

°V

A6.143 CF₂CI CH₂OCH₂CH₂

A6.144 CHF₂ CH₂OCHCH₂

A6.149 CF₂CI CHOCH₂CH₂

Comp. R₃ -R i no.

A6.154 CF₃ CH₂OCH₂CH₂

A6.156 CHF₂ CH₂OCH₂CH₂

CCHHFF..

A6.158 CF₂CI CH₂

VV CH,

A6.161 CF₂CI CH₂OCH₂CH_{2 0} P^HF=

VV'

A6.162 CHF₂ CH₂OCH₂CH₂

A6.163 CF₃ CH₂ f%

^°T>

Comp. R₃ L γ, ^R' no. V

A6.167 CF₂CI CH₂OCH₂CH₂

A6.173 CF₂CI CH₂OCH₂CH₂

A6.175 CF₃ CH₂ K

"X

A6.178 CF₃ CH₂OCH₂CH₂ , V

V>

A6.179 CF₂CI CH₂OCH₂CH₂

A6.184 CF₃ CH₂OCH₂CH₂

A6.185 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L no. v^'R'

K

A6.188 CF₂CI CH₂

T° Ks cH. N^ ³

A6.190 CF₃ CH₂OCH₂CH

T<\ CH₃ ^ ³

A6.191 CF₂CI CH₂OCH₂CH₂

A6.194 CF₂CI CH₂ V°>

A6.195 CHF₂ CH₂ V)

A6.196 CF₃ CH OCH₂CH₂ v>

A6.197 CF₂CI CH₂OCH₂CH₂ v°>

Comp. R₃ - i no.

A6.202 CF₃ CH_{2 s}^ ³

V >

A6.203 CF₂CI CH_{2 s} f^]

A6.204 CHF₂ CH_{2 s}^ f"³

A6.205 CF₃ CH₂OCH₂CH₂ PH₃ v>

A6.206 CF₂CI CH₂OCH₂CH₂ PH₃ v>

A6.207 CHF₂ CH₂OCH₂CH₂ PH₃ v N-V>

A6.210 CHF₂ CH₂ O γCH_: N^N CH₃

A6.213 CF₃ CH₂

V^>

A6.214 CF₂CI CH_{2 n} PH,

°-"- -N

A6.216 CF₃ CH₂OCH₂CH_P PH,

A6.217 CF₂CI CH₂OCH₂CH_:

A6.218 CHF₂ CH₂OCH₂CH₂

A6.219 CH₂ CF_{3 n} °^H: vv OCR

^N-N

A6.222 CH₂OCH₂CH₂ CF₃ r°

^°vv „ OCH,

A6.223 CH₂OCH₂CH₂ CF₂CI ^c vv N

OCH, N

A6.224 CH₂OCH₂CH₂ CHF₂

A6.225 CF₃ CH₂

Comp. R₃ ^•R i no.

A6.230 CCIF₂ CH

N^^

A6.235 CHF₂ CH₂

A6.242 CF₃ CH₂

T>-Q Comp. R₃ - I no.

A6.246 CF₃ CH₂ v

A6.247 CF₃ CH₂OCH₂CH₂ Vv

Table A7: Compounds of formula IAa_z:

Comp. R₃ L ^• i no.

Comp. R₃ L ' no. V

A7.010 CF₃ CH₂ VV'°

^N~- CH₃

A7.011 CF₃ CH₂OCH₂CH₂ V 1 v KCH₃

A7.012 CF₃ CH₂OCH₂CH₂ V i v^CH ₃

A7.013 CF₃ CH₂

1 —O

A7.016 CF₃ CH_{2 ς} P^H3

V> ,

Comp. R₃ L /^Rl no.

^N-R

A7.026 CF₃ CH_P

T ^cHa

Table A8: Compounds of formula IAa_g:

Comp. R₃ L /^R 1 no.

A8.002 CF₂H CH₂ PH.

V lv K^H ₃

A8.007 CF₃ CH₂ CHF₂

Vv

A8.008 CF₃ CH₂ Vv

A8.010 CF₃ CH₂ V 1V-s'°=o

^N-N^ ^SCH₃

A8.011 CF₃ CH₂OCHCH₂ Vv

A8.012 CF₃ CH₂OCH₂CH₂ Vv

A8.015 CF₂H CH₂

A8.017 CF₂CI CH₂OCH₂CH

A8.018 CHF₂ CH₂OCH₂CH CH₃ v^

A8.019 CF₂CI CH₂ CH₃

V i v^CH ₃

A8.020 CF₃ CH₂OCH₂CH₂

A8.021 CF₂CI CH₂OCH₂CH₂

A8.022 CHF₂ CH₂OCH₂CH₂

A8.025 CF₃ CH₂OCH₂CH₂

A8.026 CF₂CI CH₂OCH₂CH₂

A8.027 CHF₂ CH₂OCH₂CH₂

A8.029 CHF₂ CH₂ o Vv 1 / Comp. R₃ L /^R l l " no. 2

A8.030 CF₃ CH₂OCH₂CH₂ 0 Vv /

A8.031 CF₂CI CH₂OCH₂CH₂ 0 Vv / / y^°

A8.036 CF₃ CH₂OCH₂CH₂ 0 Vv ^/

A8.037 CF₂CI CH₂OCH₂CH₂

A8.038 CHF₂ CH₂OCH₂CH₂

^• 0 V\ ^ / y -⁰

A8.040 CF₂CI CH₂ y

Vv /

A8.041 CHF₂ CH₂

0 5" T ^N-_N o'

Comp. R₃ vr no.

R .

A8.043 CF₂CI CH₂OCH₂CH₂

. y K -o

A8.044 CHF₂ CH OCH₂CH₂

. TK y

A8.053 CF₃ CH₂OCH₂CH₂ f V y o

A8.054 CF₂CI CH₂OCH₂CH₂

A8.055 CHF₂ CH₂OCH₂CH₂

A8.057 CF₂CI CH_P P TK

Comp. R₃ L /^R 1 no.

A8.060 CF₂CI CH₂OCHCH₂ , y

TK

A8.061 CHF₂ CH₂OCH₂CH₂ , y

TV

A8.065 CF₃ CHOCH₂CH Vv N

0 y s

A8.066 CF₂CI CHOCH₂CH₂

A8.067 CHF₂ CH₂OCH₂CH₂ V Ny-

_< s

A8.072 CF₂CI CH₂OCH₂CH₂

A8.081 CF₂CI CH₂

N^^N'

A8.082 CHF, CH₂ v 7 ,

N^!N

I ,N

A8.084 CF₂CI CH₂OGH₂CH₂

A8.085 CHF₂ CH₂OCH₂CH₂

V

A8.086 CF₂CI CH₂ Vv

A8.087 CHF₂ CH₂ Vy

A8.088 CF₂CI CH₂OCH₂CH₂ vv

A8.089 CHF₂ CH₂OCH₂CH₂ v ^N-ytϊ

A8.092 CF₃ CH₂OCH₂CH₂

A8.093 CF₂CI CH₂OCH₂CH₂

A8.094 CHF₂ CH₂OCH₂CH₂

A8.098 CF₃ CH₂OCH₂CH₂ Vv

A8.099 CF₂CI CH₂OCH₂CH₂ Vy₀

A8.100 CHF₂ CH₂OCH₂CH₂ Vv

Comp. R3 ,R, no. R.

A8.102 CHF₂ CH₂ V

A8.103 CF₂CI CH₂OCH CH₂ V

A8.104 CHF₂ CH₂OCH₂CH₂

A8.105 CF₃ CH₂ VK

A8.108 CF₃ CH₂OCH₂CH₂

A8.109 CF₂CI CH₂OCH₂CH₂

A8.110 CHF₂ CH₂OCH₂CH₂ °γo. ,f F

F

N^N-- ^ F

A8.111 CF₃ CH₂

A8.112 CF₂CI CH₂ ^'T

A8.113 CHF₂ CH₂ 'T

A8.114 CF₃ CH₂OCH₂CH₂ 'V

A8.115 CF₂CI CH₂OCH₂CH₂

A8.118 CF₂CI CH₂ V KL ./ c

A8.120 CF₃ CH₂OCH₂CH₂ V c,

A8.121 CF₂CI CH₂OCH₂CH₂

A8.122 CHF₂ CH₂OCH₂CH₂ V>_α

A8.123 CF₃ CH₂

O

A8.127 CF₂CI CH₂OCH CH₂

A8.128 CHF₂ CH₂OCH₂CH₂ V-Λg÷ \ -

O

A8.129 CF₃ CH₂ °n

0* °

Comp. R₃ L no. ϊ^'R'

V

A8.133 CF₂CI CH₂OCH₂CH₂

A8.138 CF₃ CH₂OCH₂CH₂

N~O'

A8.139 CF₂CI CH₂OCH₂CH₂

A8.140 CHF₂ CH₂OCH₂CH₂

A8.143 CF₃ CH₂OCH₂CH₂

A8.144 CF₂CI CH₂OCH₂CH₂

A8.145 CHF₂ CH₂OCH CH₂ PH₃ vL

Comp. R₃ L /^R l no.

A8.148 CF₃ CH₂OCH₂CH₂

A8.149 CF₂CI CH₂OCH₂CH₂

A8.150 CHF₂ CH₂OCH₂CH

A8.151 CF₂CI CH₂ CHF₂

Vv

A8.152 CHF₂ CH₂ PHF,

Vv

A8.153 CF₃ CH₂OCH₂CH₂ PHF,

Vv

A8.154 CF₂CI CH₂OCH₂CH₂ PHF,

Vv

A8.155 CHF₂ CH₂OCH₂CH₂

A8.160 CF₂CI CH₂OCH₂CH₂ /f

A8.161 CHF₂ CH₂OCH₂CH₂

A8.166 CF₂CI CH₂OCH₂CH₂

A8.167 CHF₂ CH₂OCH₂CH₂

A8.168 CF₃ CH₂ V-

^' V^N> o

A8.172 CF₂CI CH₂OCH₂CH₂

A8.179 CHF₂ CH₂OCH₂CH₂

A8.180 CF₃ CH_P

CH,

A8.181 CF₂CI CH₂

-CH,

A8.182 CHF₂ CH₂ -' CH,

A8.183 CF₃ CH₂OCH CH₂

-CH,

A8.184 CF₂CI CH₂OCH₂CH₂

CH, i T"

A8.189 CF₃ CH₂OCH₂CH₂ °γ

A8.190 CF₂CI CH₂OCH₂CH₂

A8.191 CHF₂ CH₂OCH₂CH₂ °γq

A8.195 CF₃ CH_{2 s} P^H*

A8.196 CF₂CI CH₂ CH,

V^N>

A8.197 CHF₂ CH₂ pπ

N~

A8.198 CF₃ CH₂OCH₂CH_{2 s}^ ?^H>

A8.199 CF₂CI CH₂OCH₂CH₂ PH₃

V^N>

A8.200 CHF₂ CH OCH₂CH₂

A8.201 CF₃ CH₂

A8.207 CF₃ CH₂

^°x

A8.208 CF₃ CH₂

N_^

Comp. R₃ - i no.

A8.210 CCIF₂ CH ~

A8.211 CCIF₂ CH₂

A8.215 CHF₂ CH₂ o_^v

I

A8.218 CF₃ CH₂ ^ \J

A8.219 CHF₂ CH₂ o. / ϊ -0

A8.220 CF₃ CH₂

A8.221 CHF₂ CH₂ >-0-^c'

A8.222 CF₃ CH₂ .CF,

10^N C}

A8.223 CHF₂ CH₂ .CF, Comp. R₃ -R, no.

Table A9: Compounds of formula lAag:

Comp. R₃ L -Ri no.

Comp. R3 L /^R l no. v,

A9.006 CF₃ CH₂ PH,

V 7\o i

^N ^

A9.007 CF₃ CH₂ CHF₂

Vv

A9.010 CF₃ CH₂ V I "°

^N~~ ^ C°H₃

A9.014 CF₃ CH₂

V>

A9.020 CF₃ CH₂ O

Table A10: Compounds of formula lAa- :

Comp. R₃ L ' no. ^■s..

A10.010 CF₃ CH₂ V\ ^CH3

7 K-o

A10.014 CF₃ CH₂ CH„

Comp. R₃ ^•R, no.

A10.017 CF₃ CH₂ -o.

Table B1 : Compounds of formula IAbi

Comp. R₃ L ^• i no.

Comp. R3 -R i no.

R .

B1.009 CF₃ CH₂ vy CH,

B1.011 CF₃ CH₂OCH₂CH₂ vy CH,

B1.013 CF₃ CH₂ o. r

T N. ,F

B1.014 CF₂CI CH₂ pπ₃

T -

B1.016 CF₃ CH₂OCH₂CH₂

B1.017 CF₂CI CH₂OCH₂CH₂ ^ j p*H**_{3 ψ}

Vy F F

B1.018 CHF₂ CH₂OCH₂CH₂ o 0 ''^CCHH*^a K Comp. R₃ L no. V^'R'

V

B1.020 CF₃ CH₂OCH₂CH₂

B1.021 CF₂CI CH₂OCH₂CH₂

B1.022 CHF₂ CH₂OCH₂CH

B1.025 CF₃ CH₂OCH₂CH₂

B1.026 CF₂CI CH₂OCH₂CH₂

B1.027 CHF₂ CH₂OCH₂CH₂

B1.031 CF₂CI CH₂OCH₂CH₂ o Vv / / y °

B1.032 CHF₂ CH₂OCH₂CH₂ o Vv 1 yy° /

B1.037 CF₂CI CH₂OCH₂CH₂

B1.038 CHF₂ CH₂OCH₂CH₂

B1.039 CF₃ CH₂ Ϋ

Vy₀ ^/

B1.042 CF₃ CH₂OCH₂CH₂

TK'

B1.043 CF₂CI CH₂OCH₂CH₂ o Vy ? ₀ ^/

B1.044 CHF₂ CH₂OCH₂CH₂ o V • \ y o /

^N- ^

B1.051 CF₂CI CH_{2 o} Vy r^'

B1.052 CHF₂ CH₂ vy y

B1.053 CF₃ CH₂OCH₂CH_{2 n} f

Vy y

B1.054 CF₂CI CH₂OCH₂CH₂ /-~ y

B1.055 CHF₂ CH₂OCH₂CH₂ f

Vy

B1.060 CF₂CI CH₂OCH₂CH₂

B1.061 CHF₂ CH₂OCH₂CH₂

B1.065 CF₃ CH₂OCH₂CH₂ V N-vK Ni o K-s

B1.066 CF₂CI CH₂OCH₂CH V N-vK Ni o K-s

B1.067 CHF₂ CH₂OCH₂CH₂ o. vv N

< s o

B1.072 CF₂CI CH₂OCH₂CH

Comp. R3 L no. v^'R'

V

B1.078 CF₂CI CH₂OCH₂CH₂

B1.080 CF₃ CH₂

I ,N -^

B1.081 CF₂CI CH₂

1/

B1.082 CHF₂ CH₂

I .N -^

B1.083 CF₃ CH₂OCH₂CH₂

7 ,N N-^

B1.084 CF₂CI CH₂OCH₂CH₂ N

B1.086 CF₂CI CH₂ Vy

B1.087 CHF₂ CH₂ Vv Comp. R₃ L no. v'^R'

K

B1.088 CF₃ CH₂OCH₂CH₂ vv

B1.089 CF₂CI CH₂OCH₂CH₂ vv

B1.090 CHF₂ CH OCH CH₂ vy

B1.093 CF₃ CH₂OCHCH₂

B1.094 CF₂CI CH₂OCH CH₂

B1.095 CHF₂ CH₂OCH₂CH

B1.096 CF₃ CH₂ V lvo

B1.097 CF₂CI CH₂ Vv

B1.099 CF₃ CH₂OCH CH₂ V ^■VT o ^\

B1.100 ^• CF₂CI CH₂OCH CH

B1.101 CHF₂ CH₂OCH₂CH₂ Vv

B1.105 CF₂CI CH₂OCH₂CH₂ V°;

B1.106 CHF₂ CH₂OCH₂CH₂ Y

B1.108 CF₂CI CH₂ YK

B1.109 CHF₂ CH₂ v°κ

B1.110 CF₃ CH₂OCH₂CH₂ VK F F

B1.111 CF₂CI CH₂OCH₂CH₂

B1.112 CHF₂ CH₂OCH₂CH₂

^N~N F

B1.113 CF₃ CH₂ °V

B1.114 CF₂CI CH₂

B1.116 CF₃ CH₂OCH₂CH₂ V N-g>/

B1.117 CF₂CI CH₂OCH₂CH₂ °V

B1.118 CHF₂ CH₂OCH₂CH₂ °V

B1.120 CF₂CI CH₂ Λ -cι

B1.121 CHF₂ ^{CHi! Q} ^'T' K - -CI Comp. R₃ L /^R1 no. V

B1.122 CF₃ CH₂OCH CH₂ V α

B1.123 CF₂CI CH₂OCH₂CH₂ Vy

B1.124 CHF₂ CH₂OCHCH₂ ^°Y

B1.125 CF₃ CH₂

N-g- o

B1.127 CHF_? CH₂ V\ o

B1.129 CF₂CI CH₂OCH₂CH₂

B1.130 CHF₂ CHOCH₂CH₂ V N-gv*

\ _ o

B1.134 CF₃ CH₂OCH₂CH₂ ^°v>

6' °

B1.135 CF₂CI CH₂OCH CH₂ ^°n N_^ ' 0* °

B1.138 CF₂CI CH₂

B1.141 CF₂CI CH₂OCH₂CH₂

B1.142 CHF₂ CH₂OCH₂CH₂

B1.145 CF₃ CH₂OCH₂CH₂

B1.146 CF₂CI CH₂OCH₂CH₂

B1.147 CHF₂ CH₂OCH₂CH₂

B1.150 CF₃ CH₂OCH₂CH₂

Comp. R₃ L /^R 1 no. K

B1.151 CF₂CI CH₂OCH₂CH₂

B1.152 CHF₂ CH₂OCH₂CH₂

B1.155 CF₃ CH₂OCH₂CH₂

B1.156 CF₂CI CH OCH₂CH₂

B1.157 CHF₂ CH₂OCH₂CH₂

.161 CF₃ CH₂OCH₂CH₂

Comp. R₃ L no. R ₂

B1.162 CF₂CI CH₂OCH CH f

B1.168 CF₂CI CH₂OCH₂CH₂

B1.169 CHF₂ CH₂OCH₂CH₂

B1.170 CF₃ CH₂ y

V o

Comp. R₃ L no. v'ⁿ'

V

B1.174 CF₂CI CH₂OCH₂CH₂ vC

0

B1.175 CHF₂ CH₂OCH₂CH₂ vV o

B1.179 CF₃ CH₂OCH₂CH₂

B1.180 CF₂CI CH₂OCH₂CH₂

Comp. R₃ L /^R 1

I ¹ no.

B1.183 CF₂CI CH₂ 7 Ken.

N^ ³

B1.186 CF₂CI CH₂OCH₂CH₂

B1.188 CF₃ CH₂ -

CH₃

B1.189 CF₂CI CH₂ V N-> CH₃

B1.190 CHF₂ CH₂ v N_^°>

GH₃

B1.191 CF₃ CH₂OCH₂CH₂ v N^°/> CH₃

B1.192 CF₂CI CH₂OCH₂CH₂

N-

CH₃

B1.193 CHF₂ CH₂OCH₂CH₂ V N^⁵/) CH₃

B1.195 CF₂CI CH₂ Vy

B1.196 CHF₂ CH₂ V Comp. R₃ L γ^'R' no. V

B1.197 CF₃ CH₂

V^N>

B1.200 CF₃ CH₂OCH₂CH₂ PH₃

V N^^N>

B1.201 CF₂CI CH₂OCH₂CH₂ H₃

V^N>

B1.202 CHF₂ CH₂OCH₂CH₂

B1.205 CHF₂ CH₂

°T}

Comp. R₃ L -R i no.

B1.211 CF₃ CH₂ CH,

V

B1.212 CF₂CI CH₂ o '^CH*

Y\

B1.214 CF₃ CH₂OCH₂CH_{2 0} F^

B1.215 CF₂CI CH₂OCH₂CH_{2 0χ} j*³

V^N>

B1.216 CHF₂ CH₂OCH₂CH_{2 0} f^H*

N~

B1.220 CH₂OCH₂CH₂ CF₃

B1.221 CH₂OCH₂CH₂ CF₂CI

B1.222 CH₂OCH₂CH₂ CHF₂

B1.223 CF₃ CH₂ N- Comp. R₃ L /^R 1 no. V^'

K

B1.224 CF₃ CH₂OCH₂CH₂

N^

B1.225 CF₃ CH₂

^

B1.226 CF₃ CH₂ ^y

B 1.229 CCIF₂ CH₂

^°b

B1.230 CCIF₂ CH₂

N^/

B1.231 CCIFp CH₂

B1.236 CF₃ CH₂ v< - "

Comp. R₃ /^H1 no.

B1.244 CF, CH₂

N — /

Table B2: Compounds of formula IAb_?

Comp. R₃ /R i no.

B2.006 CF₃ CH₂ , vy '^CH3 ₀ CH,

B2.008 CF₃ CH₂ vy CH,

B2.009 CF₃ CH₂ Vy CH,

B2.010 CF₃ CH₂ V_V'° N^N CR,

Comp. R₃ -Ri no.

2

Table B3: Compounds of formula IAb₃:

Comp. R₃ -RI Phys. no. data

Comp. R₃ L /^R l Phys. no. V data

B3.008 CF₃ CH₂ V 1 KcR

^{N 3}

B3.012 CF₃ CH₂ CH,

°K 1 N

M ''

.

B3.016 CF₃ CH₂ CH_g

B3.017 CF₃ CH₂ v>

B3.019 CF₃ CH₂

Y M —] I

Table C1 : Compounds of formula IAcι_:

C1.001 CF₃ CH₂ CH₃ N.

I H

C1.009 CF₃ CH₂ vy

C1.010 CF₃ CH₂ V\ >?

^N~-N CH₃

C1.011 CF₃ CH₂ V l ^S K- o^CH3 Comp. R₃ ^•R , no.

C1.012 CF₃ CH₂ CH,

O.

V ,N

N-^

C1.015 CF₃ CH₂ ,^CH3

C1.020 CF₃ CH₂ °.

N M — I

Table C2: Compounds of formula lAc?:

Comp. R₃ L - i Phys. no. data

C2.008 CF₃ CH₂ Vy CH,

C2.009 CF₃ CH₂ V iv*

C2.011 CF₃ CH₂ O / υomμ. π₃ -R , Phys. no. data

C2.014 CF₃ CH₂ CH,

Y^N>

C2.017 CF₃ CH₂

3

Comp. R₃ -R i Phys. no. data

Table D1 : Compounds of formula lAd:

Comp. R₃ ^•R i no.

D1.008 CF₃ CH₂ Vy CH,

D1.009 CF₃ CH₂ Vy

CH₂ O.s

D1.010 CF₃

^N~-N CH,

D1.013 CF₃ CH₂ CH₃

I .N

N- N

D1.018 CF₃ CH₂ ° 5s^O

D1.019 CF₃ CH₂ ° \

D1.020 CF₃ CH₂ °x

N— '

Comp. R₃ L -R i no.

Preferred synergistic mixtures according to the invention comprise the active ingredient combinations described in the following Table, the compounds of formula I that are used being the compounds of formula la (no. A1.230 according to Table A1 ) or of formula lb (no. A1.219 according to Table A1 ) or of formula lc (no. A1.213 according to Table A1):

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

Name Pesticide Manual 12 ed., entry no. prosulfocarb 656 pyraflufen-ethyl 662 mesotrione 500 fenoxaprop-P-ethyl 331 dichiorprop 228

MCPA 485

MCPB 487 isoxaflutole 467 nicosulfuron 560 primisulfuron-methyi 633 sulcotrione 710 clodinafop-propargyl 156 picolinafen 621 beflubutamid 57 flucarbazone 357 cyhalofop-butyl 191 mecoprop 489 diclofop-methyl 232 amidosulfuron 24 flupyrsulfuron 374 flupyrsulfuron-methyl-sodium 374 Name Pesticide Manual 12^th ed., entry no.: metsulfuron-methyl 536 sulfosulfuron 714 tribenuron-methyl 778 imazamethabenz-methyl 438 chlortoluron 142 isoproturon 464 methabenzthiazuron 510 bifenox 75 fluoroglycofen-ethyl 371 imazosulfuron 444 diflufenican 245 bilanafos 77 ethalfluralin 298 trifluralin 791 fluthiamid 362 isoxaben 466 trialiate 772

2,4-DB 211

MCPP 489 mecoprop-P 490 clopyralid 162 fluroxypyr 380 quinmerac 682 dicamba 222 procarbazone 541 glufosinate 406 fluthiacet 385 imazamox 439 imazethapyr 443 rimsulfuron 689 halosulfuron 414 cloransulam 164 flumiclorac 367 Name Pesticide Manual 12^th ed., entry no. clomazone 159 diclosulam 235

2,4-D and its salts 205 florasulam 351 bromoxynil 93 sethoxydim 694 ioxynil 455 tepraloxydim 735 carfentrazone 119 clethodim 155 sulfentrazone 711 imazaquin 442 imazapyr 441 mesotrione 500 thifensulfuron 754 prosulfuron 657 bentazone 69 iodosulfuron 454 prohexadione 639 diflufenzopyr 246 flurtamone 382 butylate 106 flumioxazin 368 fentrazamide 340 fluazolate 355 aclonifen 10 cinidon-ethyl 152 glyphosate 407 paraquat 592 azafenidin 43 terbuthylazine 739 amicarbazone 23 benazolin-ethyl 59 Name Pesticide Manual 12^th ed., entry no.: difenzoquat 242 dithiopyr 275 quinclorac 681 prodiamine 637 benefin 61 trifluralin 791 tralkoxydim 767 chlorsulfuron 146 triasulfuron 773 flamprop-M 348 metoxuron 534

Flufenpyr-ethyl (2-chloro-5-[1 ,6-dihydro-5-methyl-6-oxo-4-(trifluoromethyl)pyridazin-1 -yl]-4- fluorophenoxyacetic acid ethyl ester) is registered under Chemical Abstracts No. 188490-07-5. Benf lubutamid (2-[4-f luoro-3-(trif luoromethyl)phenoxy]-N-(phenylmethyl)- butanamide) is registered under Chemical Abstracts No. 113614-08-7. Mesosulfuron is described under Chemical Abstracts Registry No. 208465-21-8. The compound of formula II and its preparation are known from WO 99/47525. Isopropazole (5-[4-bromo-1-methyl-5- (trifluoromethyl)-l H-pyrazol-3-yl]-2-chloro-4-fluoro-benzoic acid isopropyl ester) is known from Moss, S. R. and M. Rooke S. 1997, Activity of JV 485, a protoporphyrinogen oxidase inhibitor, on herbicide-resistant black-grass (Alopecurus myosuroides), 1997 Brighton crop protection conference: weeds. Proceedings of an international conference, Brighton, UK, 17-20 November 1997. 1 : 337-342.

Benzfendizone (2-(5-ethyl-2-{4-[1 ,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-(trifluoro- methyl)pyrimidin-1 -yl]phenoxymethyl}phenoxy)propionic acid ethyl ester is registered under Chemical Abstracts No. 158755-95-4. Isoxachlortole (4-chloro-2-mesylphenyl 5-cyclopropyl- 1 ,2-oxazol-4-yl ketone) is registered under Chemical Abstracts No. 141112-06-3. Tritosulfuron (Λ/-[[[4-methoxy-6-(trifluoromethyl)-1 ,3,5-triazin-2-yl]amino]carbonyl]-2- (trifluoromethyl)benzenesulfonamide) is described under Chemical Abstracts No. 142469-14-5 and is also known from EP-A-559 814. Glufosinate is preferably used in accordance with the invention in the form of salts, especially the ammonium salt. Special preference is given to use of the L-isomer of glufosinate. Preferably, prohexadione is used in the form of the calcium salt and procarbazone in the form of the sodium salt. Fluthiacet, thifensulfuron, iodosulfuron, cloransulam and halosulfuron are used especially in the form of the methyl ester. Carfentrazone is used in the form of the ethyl ester. Flumiclorac is used in the form of the pentyl ester. Ketospiradox is described in Chemical Abstracts under the Registry No. CAS 192708-91-1 and aminopyralid is known from AGROW (2002) Newsletter, 4th September 2002.

The composition according to the invention comprises the active ingredient of formula I and one or more active ingredients selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin in any mixing ratio, but usually has an excess of one component over the other. In general the mixing ratios (by weight) between the active ingredient of formula I and the mixing partners pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

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

The mixtures of the compound of formula I with the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 to say 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, combinations of a suspension and emulsion (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 active ingredients of formula I and pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 per se, 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 include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.

The amounts of oil additive used in the composition according to the invention are generally from 0.01 to 2 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, 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, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Special preference is given to "Additive Type A", which contains as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight 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 Cι₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-1 1 1 - 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 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 on pages 7 and 8 of WO 97/34485.

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 surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.

Preference is also given to the use, as surface-active substances, of silicone surfactants, especially polyalkyl oxide-modified heptamethyltrisiloxanes, which are commercially available, for example, as Silwet L-77®, and also perfluorinated surfactants. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) and, more especially, Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types. The concentration of such 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. A preferred oil additive is known by the name MERGE®, can be purchased from the BASF Corporation and is essentially described, for example, in US-A-4,834,908 in col. 5, as Example COC-1. A further preferred oil additive is SCORE® (Novartis Crop Protection Canada.)

In addition to the oil additives listed above, it is also possible, for the purpose of enhancing the action of the compositions according to the invention, to add formulations of alkyl pyrrolidones, as are sold commercially, for example, as Agrimax®, to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p-menthene, as are marketed, for example, as Bond®, Courier® or Emerald®, can also be used for the purpose of enhancing the action. Solutions comprising propionic acid, for example Eurogkem Pen-e-trate®, can also be admixed as action-enhancing agents with the spray mixture.

The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising the compounds of formula I together with the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and 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 in the form of concentrates will usually be preferred, 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), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. The compositions according to the invention are preferably used in the presence of a nitrogen source. Such nitrogen sources are described, for example, in EP-A-0 584 227. A suitable nitrogen source is NITRO-30® SRN (30-0-0; 10.38 lbs/gal, 3.1 lbs of N/gal), a delayed- release nitrogen-containing solution having a content of 85 % nitrogen in the form of methylene urea. NITRO-30® is commercially available and can be purchased, for example, from Monterey Chemical Co., Fresno, CA 93745-5000, USA. Preferred formulations have especially the following compositions: (% = % 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, but do not limit the invention. 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 % arom. hydrocarbon mixture 85% 78% 55% 16%

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 20% 10% _ _

N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 %

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 active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then 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) e.g. CaCO₃ or SiO₂

The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

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 and ground with the adjuvants, and the mixture is moistened with water. The mixture is 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 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 %

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 compounds of formula I and the mixing partner or partners selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr- ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclof op-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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, 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). The composition according to the invention may also comprise fungicides, 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 ). The number in parentheses after each active ingredient refers to the respective entry number for that active ingredient 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 a compound of formula I and one or more active ingredients selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 (cf. COLBY, S.R., "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22, 1967):

We = X + [Y » {l00- X) / 10 ]

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 selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 compound of formula I and a compound selected from the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr- ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 active ingredients of formula I with the active ingredients pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, phmisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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.

Test description, pre-emergence test:

Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension, are applied by spraying (500 litres of water per ha). The rates of application depend on the optimum concentrations ascertained under field conditions and greenhouse conditions. The test plants are then grown in a 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.

Test description, post-emergence test:

The test plants are grown in plastics pots under greenhouse conditions to the 2- to 3-leaf stage. A standard soil is used as cultivation substrate. At the 2- to 3-leaf stage, the herbicides are applied alone and in the form of a mixture to the test plants. The application is carried out using an aqueous suspension of the test compounds in 500 litres of water per ha. The rates of application depend on the optimum concentrations 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.

It has been found, surprisingly, that specific safeners are suitable for mixing with the synergistic composition according to the invention. The present invention therefore relates also to a selectively herbicidal composition for the control of grasses and weeds in crops of useful plants, especially in crops of maize, which composition comprises a compound of formula I, one or more compounds selected from the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycof en-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and and a safener (counter-agent, antidote) and protects the useful plants, but not the weeds, against the phytotoxic action of the herbicide, and also to the use of such a composition in controlling weeds in crops of useful plants.

In accordance with the invention there is also accordingly proposed a selectively herbicidal composition which, 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 a compound of formula I and one or more compounds selected from the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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

the salts or 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 the methyl and ethyl esters and salts thereof,

and of formula 3.13

and of formula 3.14

and of formula 3.15

H₃C O and of formula 3.16

H₃C

and of formula 3.17

and of formula 3.18

and of formula 3.19

The invention relates also to a selectively herbicidal composition which, 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 a compound of formula I 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

the salts or 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 the methyl and ethyl esters 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

and of formula 3.18

and of formula 3.19

Preferred compositions according to the invention comprise a compound of formula la, lb or lc, each in combination with 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, 3.17, 3.18 and 3.19.

The invention relates also to a method of selectively controlling weeds in crops of useful plants, which comprises treating the useful plants, seeds or seedlings thereof, or the area of cultivation thereof, with a herbicidally effective amount of a herbicide of formula I, optionally one or more herbicides selected from the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and and an amount, effective for herbicide antagonism, of a safener selected from the compounds of formulae 3.1 to 3.19.

The compounds of formulae 3.1 to 3.19 are known and are described, for example, in The Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under entry numbers 61 (formula 3.1 , benoxacor), 304 (formula 3.2, fenclorim), 154 (formula 3.3, cloquintocet- mexyl), 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 by the name 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 compound of formula 3.12 (isoxadifen, 4,5-dihydro-5,5-diphenyl-1 ,2-oxazole-3-carboxylic acid) is described under Chemical Abstracts No. 209866-92-2 and in DE-A-4 331 448, and the compound of formula 3.13 is described 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 other 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 also suitable for the protection of 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. Compounds 3.18 and 3.19 are known from WO 04/021788.

As crop plants that can be protected by the safeners of formulae 3.1 to 3.19 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, very especially cereals. Crops are to be understood as including those that have been made tolerant to herbicides or classes of herbicides by means of conventional breeding or genetic engineering methods. Examples of such crops are glyphosate- or glufosinate- or L- glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

Crops are to be understood as also including those that have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-0 451 878, EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529.

The weeds to be controlled may be either monocotyledonous or 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 are areas of land on which the crop plants are already growing or in which the seed material of those crop plants has been sown, and also land on which it is intended to grow those crop plants. A safener of formula 3.1 to 3.19 may, depending on the intended use, be used to pre-treat the seed material of the crop plant (dressing the seed or the seedlings) or may be incorporated into the soil before or after sowing. It may, however, also be applied, alone or together with the herbicide, after the emergence of the plants. The treatment of the plants or seed material with the safener can therefore, in principle, be effected independently of the time at which the herbicide is applied. The treatment of the plants can, however, also be carried out by applying the herbicide and safener simultaneously (for example in the form of a tank mixture). The rate of application of the safener in relation to the herbicide depends largely on the method of application. In the case of field treatment, which is carried out either by 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, from 0.001 to 1.0 kg of safener per hectare, preferably from 0.001 to 0.25 kg of safener per hectare, is generally applied.

The rates of application of herbicides are 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 per kg of seed, preferably from 0.05 to 2 g of safener per kg of seed, are applied. If the safener is applied in liquid form, by seed soaking, shortly before sowing, it is advantageous to use safener solutions containing the active ingredient in a concentration of from 1 to 10 000 ppm, especially from 100 to 1000 ppm.

For application, the safeners of formula 3.1 to 3.19 or combinations of those safeners with the herbicide of formula I and, optionally, one or more herbicides selected from the compounds pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr- ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin are advantageously processed together with the adjuvants customary in formulation technology into formulations, for example into emulsifible concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.

Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. The formulations are prepared in known manner, for example by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants such as, for example, solvents or solid carriers. It is also possible additionally to use surface-active compounds (surfactants) in the preparation of the formulations. Solvents and solid carriers suitable for that purpose are mentioned, for example, on page 6 of WO 97/34485.

Depending on the nature of the active ingredient 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 used 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 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 pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methy], rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and and the compounds of formula 3.1 to 3.19, 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 concentrates are usually preferred as commercial products, 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), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. For the use of safeners of formula 3.1 to 3.19 or of compositions comprising them for the protection of crop plants against harmful effects of herbicides selected from the compounds of formula I, pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and various methods and techniques are suitable; the following are examples:

i) Seed dressing a) Dressing the seeds with a wettable powder formulation of active ingredient of formula 3.1 to 3.19 by shaking in a vessel until the formulation is uniformly distributed over the seed surface (dry dressing). Approximately from 1 to 500 g of active ingredient of formula 3.1 to 3.19 (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed material. b) Dressing the seeds with an emulsifiable concentrate of active ingredient of formula 3.1 to 3.19 according to method a) (wet dressing). c) Dressing by immersing the seed material in a liquid formulation comprising from 100 to 1000 ppm of active ingredient of formula 3.1 to 3.19 for from 1 to 72 hours and, if desired, subsequently drying the seeds (immersion dressing). Dressing the seed material or treating the germinated seedlings are naturally the preferred methods of application because the treatment with active ingredient is directed wholly 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 material, although, depending on the method employed, which also allows the addition of other active ingredients or micronutrients, amounts above or below the specified concentration limits may be employed (repeat dressing).

ii) Application in the form of a tank mixture

A liquid formulation of a mixture of antidote and herbicide (ratio of the one to the other from 10:1 to 1 :100) is used, 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 active ingredients of formula 3.1 or 3.2 are introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, a wettable powder or granules. After the seed furrow has been covered, the herbicide is applied pre-emergence in the normal manner.

iv) Controlled release of the active ingredient

The active ingredients of formulae 3.1 to 3.19 are applied in solution to granulated mineral carriers or polymerised granules (urea-formaldehyde) and dried. If desired, a coating may be applied (coated granules) which enables the active ingredient to be released in metered amounts over a predetermined period of time.

Preferred formulations have especially the following compositions (% = percent by weight)

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 %

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

Formulation examples for mixtures comprising herbicides of formula I. optionally compounds selected from pyridafol. dicamba and its salts, procarbazone. benflubutamid. tralkoxydim, mesosulfuron, chlorsulfuron. triasulfuron, -flamprop-M. metoxuron. glufosinate. L-glufosinate. fluthiacet. imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron. halosulfuron. cloransulam. clomazone. diclosulam. 2,4-D and its salts, florasulam, flumiclorac. bromoxynil. sethoxydim. ioxynil, tepraloxydim, carfentrazone. clethodim. sulfentrazone, imazaguin. sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone. iodosulfuron. prohexadione, diflufenzopyr. flurtamone. butylate. flumioxazin. fentrazamide. benzfendizone, isopropazole. fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium. ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraguat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr- ethyl, the compound of formula II

and the compounds clodinafop-propargyl. prosulfocarb. picolinafen, pyraflufen-ethyl. beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone. chlortoluron. isoproturon. methabenzthiazuron. bifenox, fluoroglycof en-ethyl, imazosulfuron. diflufenican. bilanafos, ethalfluralin. fluthiamide, isoxaben. trialiate. 2.4-DB. dichiorprop. MCPA. MCPB. mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, guinmerac, benazolin-ethyl, difenzoguat, cyhalofop-butyl, dithiopyr, guinclorac, prodiamine, benefin and and safeners of formulae 3.1 to 3.19 (% = % 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 % Ό arom. hydrocarbon mixture 85 % 78 % 55 % 16 % o

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 20% 10% - _

N-methyl-2-pyrrolidone - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 %

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

(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.

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

The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then 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) e.g. CaCO₃ or SiO₂

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% - (15 mol of ethylene oxide) sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1 % 1 % 1 % 1 % 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 active ingredients of formulae I, pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and and 3.1 to 3.19 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 3.19 to protect cultivated plants against the phytotoxic action of herbicides of formula I, pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, MCPA, MCPB, mecoprop, MCPP, mecoprop-P, clopyralid, fluroxypyr, quinmerac, benazolin-ethyl, difenzoquat, cyhalofop-butyl, dithiopyr, quinclorac, prodiamine, benefin and trifluralin is illustrated in the following Examples. Biological Example: Safener action

The test plants are grown to the 4-leaf stage in plastics pots under greenhouse conditions. At that stage both the herbicides alone and also the mixtures of the herbicides with the substances being tested as safeners, are applied to the test plants. The application is carried out using an aqueous suspension of the test substances prepared from a 25 % wettable powder (Example F3, b)) or from a suspension concentrate as in Example F8, using 500 litres of water per hectare. 9 days after application, the phytotoxic action of the herbicides on the crop plants such as, for example, cereals is evaluated using a percentage scale. 100 % means that the test plant is completely dead; 0 % means that there is no phytotoxic action. The mixtures according to the invention show good activity in this test. Examples of the good safener action of the compounds of formulae 3.1 to 3.19 with the compounds of formula I (increase in the selectivity of the herbicide) are given in the following Table BS1 :

Table BS1 : Increase in the selectivity of a compound of formula I by combining with a compound of formula 3.1 to 3.19 to form the composition according to the invention:

Claims

What is claimed is:

1. A selectively herbicidal composition which comprises, as active ingredient, a mixture of a) a herbicidally effective amount of a compound of formula I

wherein

L is either a direct bond, an -O-, -S-, -S(O)-, -SO₂-, -N(R_5a)-, -SO₂N(R_5b)-, -N(R_5b)SO₂-, -C(O)N(R_5c)- or -N(R_5c)C(O)- bridge, or a CrC₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain which may be mono- or poly-substituted by R₅ and/or interrupted once or twice by an -O-, -S-, -S(O)-, -SO₂-, -N(R_5d)-, -SO₂N(R_5e)-, -N(R_5e)SO₂-, -C(O)N(R_5t)- and/or -N(R_5f)C(O)- bridge, and when two such bridges are present those bridges are separated at least by one carbon atom, and, when the bridge L is bonded to a nitrogen atom of W, W is bonded to L by way of a carbon atom or a -N(R_5e)SO₂- or -N(R_5f)C(O)- bridge; W is a 4- to 7-membered, saturated, partially saturated or unsaturated ring system U

which contains a ring element Ui, and may contain from one to four further ring nitrogen atoms, and/or two further ring oxygen atoms, and/or two further ring sulfur atoms and/or one or two further ring elements U₂, and the ring system U may be mono- or poly-substituted at a saturated or unsaturated ring carbon atom and/or at a ring nitrogen atom by a group R₈, and two substituents R₈ together are a fused-on or spirocyclic 3- to 7-membered further ring system which may be unsaturated, partially saturated or fully saturated and may in turn be substituted by one or more groups R_8a and/or interrupted once or twice by a ring element -O-, -S-, -N(R_8b)- or -C(=O)-; and

Ui and U₂ are, each independently of the other(s), -C(=O)-, -C(=S)-, -C(=NR₆)-, -(N=0)-, -S(=O)- or -SO₂-;

R₃ and R₄ are, each independently of the other, C Csalkyl, C C₃haloalkyl, d-C₃alkoxy- d-Csalkyl, hydrogen, hydroxy, mercapto, halogen, CrC₃alkoxy, d-Cshaloalkoxy, d-Cjsalkoxy-Crdalkoxy, d-C₃alkylthio, CrC₃alkylsulfinyl, d-C₃alkylsulfonyl, d-C₃halo- alkylthio, d-C₃haloalkylsulfinyl, d-C₃haloalkylsulfonyl or C C₃alkylsulfonyloxy; R₅ is halogen, C C₃alkyl, C C₃alkoxy, d-C₃alkylthio, Cι-C₃alkylsulfinyl, d-dsalkylsulfonyl, d-C₃alkoxy-d-C₃alkyl or Cι-C₃alkoxy-d-C₃alkoxy;

Rs_a, Rs_b and R_5e are independently hydrogen, Cι-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl or d-Cgalkoxy-d-Csalkyl;

R_5d is hydrogen, d-C₆alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, d-C₃alkoxy-CrC₃alkyl, benzyl, cyano, formyl, C C₄alkylcarbonyl, d-C₄alkoxycarbonyl, Cι-C₄alkylsulfonyl or phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by R₇; R_5o and R_5f are, each independently of the other, hydrogen or d-C₃alkyl; R₆ is CrCealkyl, hydroxy, d-C₆alkoxy, cyano or nitro;

R₇ is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, Cι-C₃alkoxy, CrC₃haloalkoxy, cyano or nitro; each R₈ is, independently of any other, hydrogen, halogen, CrCealkyl, d-C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, C C₆alkoxy, CrC₆haloalkoxy, C₃-C₆alkenyIoxy, C₃-C₆alkynyloxy, Cι-C₃alkoxy-Cι-C₃alkoxy, mercapto, d-C₆alkylthio, CrC₆alkylsulfinyl, d-C₆alkylsulfonyl, d-C₆alkylsulfonyloxy, d-C₆haloalkylsulfonyloxy, C₃-C₆alkenylthio, C₃-C₆alkynylthio, amino, CrC₆alkylamino, di(d-C₆alkyl)amino, d-C₃alkoxy-CrC₃alkyl, formyl, d-C₄alkylcarbonyl, CrC₄alkoxycarbonyl, benzyloxycarbonyl, d-C₄alkylthiocarbonyl, carboxy, cyano, carbamoyl, phenyl, benzyl, heteroaryl or heterocyclyl, it being possible for the phenyl, benzyl, heteroaryl and heterocyclyl groups to be mono- or poly-substituted by R_7a; each R_7a is, independently of any other, halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, C C₃haloalkoxy, cyano or nitro; each R_8a is, independently of any other, halogen, C C₆alkyl, C C₆haloalkyl, C₃-C₆cycloalkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, hydroxy, Cι-C₆alkoxy, d-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, d-C₆alkylthio, d-C₆alkylsulfinyl, d-Cealkylsulfonyl, d-C₄alkyl- carbonyl, d-C₄alkoxycarbonyl, cyano or nitro;

R_8b is hydrogen, d-C₃alkyl, C₃-C₆alkenyl, C₃-C₆alkynyl, d-dalkoxy-d-Csalkyl or benzyl, it being possible for the phenyl group to be substituted by R_7b;

R_7b is halogen, C C₃alkyI, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro; p is O or l ; r is 1 , 2, 3, 4, 5 or 6; with the provisos that a) R₈ and R_8a as halogen or hydrogenmercapto cannot be bonded to a nitrogen atom, b) d as -C(=O)- or -C(=S)- does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group by way of a Cι-C₄alkylene, C₂-C₄alkenylene or C₂-C₄alkynylene chain L that is interrupted by -O-, -S-, -S(O)-, -SO₂-, -N(Rsd)-, -SO₂N(R_5e)- or by -N(R_5e)SO₂-, c) Ui as -C(=S)- does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group by way of a -CH=CH- or -C≡C- bridge L or by way of a d-C₄alkylene chain L that is interrupted by -O-, -S-, -S(O)-, -SO₂- or by -N(d-C₄alkyl)-, d) d as -C(=S)- or -C(=NR₆)- wherein R₆ is C C₆alkyl or d-C₆alkoxy does not form a tautomeric form with a substituent R₈ as hydrogen when the radical W is linked to the pyridyl group directly or by way of a C C₄alkylene chain L; either

Q is a group Q-,

wherein

A_T is C(R₁₁R₁₂) or NR₁₃;

A₂ is C(R₁₄R₁₅)_m, C(O), oxygen, NR₁₆ or S(O)_q;

A₃ is C(R₁₇R₁₈) or NR₁₉; with the proviso that A₂ is other than S(O)_q when A-i is NR ₃ and/or A₃ is NRι₉;

Xi is hydroxy, O^"M⁺ wherein M⁺ is a metal cation or an ammonium cation; halogen or

S(O)_nR₉, wherein m is 1 or 2; q, n and k are, each independently of the others, 0, 1 or 2;

R₉ is d-Cι₂alkyl, C₂-C₁₂alkenyl, C₂-C₁₂alkynyl, C₃-C₁₂allenyl, C₃-C₁₂cycloalkyl, C₅-C₁₂cyclo- alkenyl, R₁₀-CrC₁₂alkylene or R₁₀-C₂-Cι₂alkenylene, wherein the alkylene or alkenylene chain may be interrupted by -O-, -S(O)_k- and/or by -C(O)- and/or mono- to penta-substituted by R₂₀; or phenyl, which may be mono- to penta-substituted by R_7c; R_7c is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, Cι-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro;

R₁₀ is halogen, cyano, rhodano, hydroxy, C C₆alkoxy, C₂-C₆alkenyloxy, C₂-C₆alkynyloxy, d-C₆alkylthio, d-C₆alkylsulfinyl, C C₆alkylsulfonyl, C₂-C₆alkenylthio, C₂-C₆alkynylthio, Cι-C₆alkylsulfonyloxy, phenylsulfonyloxy, C C₆alkylcarbonyloxy, benzoyloxy, C C₄alkoxy- carbonyloxy, d-C₆alkylcarbonyl, d-C₄alkoxycarbonyl, benzoyl, aminocarbonyl, d-C₄alkyl- aminocarbonyl, C₃-C₆cycloalkyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl; it being possible for the phenyl-containing groups in turn to be substituted by R_7d; R_7d is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro;

R₂₀ is hydroxy, halogen, d-C₆alkyl, C C₆alkoxy, C C₆alkylthio, d-C₆alkylsulfinyl, CrC₆alkylsulfonyl, cyano, carbamoyl, carboxy, C C₄alkoxycarbonyl or phenyl; it being possible for phenyl to be substituted by R_7e;

R_7e is halogen, d-C₃alkyi, d-C₃haloalkyl, hydroxy, Cι-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro;

Rn and R₁₇ are, each independently of the other, hydrogen, C C₄alkyl, C₂-C₄alkenyl, C₂-C₄alkynyl, Cι-C₄alkylthio, C C₄alkylsulfinyl, C C₄alkylsulfonyl, Cι-C₄alkoxycarbonyl, hydroxy, d-C₄alkoxy, C₃-C₄alkenyloxy, C₃-C alkynyloxy, hydroxy-C C₄alkyl, C C₄alkyl- sulfonyloxy-C C₄alkyl, halogen, cyano or nitro; or, when A₂ is C(R₁₄R ₅)_m, R₁₇ together with Rn forms a direct bond or a d-C₃alkylene bridge;

R₁₂ and R ₈ are, each independently of the other, hydrogen, C C alkyl or d-C₄alkylthio, d-C₄alkylsulfinyl or d-C₄alkylsulfonyl; or R₁₂ together with Rn, and/or R-ι₈ together with R₁₇ form a C₂-C₅alkylene chain which may be interrupted by -O-, -C(O)-, -O- and -C(O)- or by -S(O)_r;

R₁₃ and R₁₉ are, each independently of the other, hydrogen, C C₄alkyl, d-C₄haloalkyl, C₃-C₄alkenyl, C₃-C₄alkynyl or Cι-C₄alkoxy;

R-ι₄ is hydrogen, hydroxy, d-C₄alkyl, CrC₄haloalkyl, d-C₃hydroxyalkyl, C C alkoxy-d-C₃- alkyl, d-dalkylthio-d-Csalkyl, CrC₄alkylcarbonyloxy-d-C₃alkyl, C C alkylsulfonyloxy- CrC₃alkyl, tosyloxy-d-C₃alkyl, di(d-C₄alkoxy)-CrC₃alkyl, C C alkoxycarbonyl, C₃-C₅- oxacycloalkyl, C₃-C₅thiacycloalkyl, C₃-C₄dioxacycloalkyl, C₃-C₄dithiacycloalkyl, C₃-C₄oxa- thiacycloalkyl, formyl, Cι-C₄alkoxyiminomethyl, carbamoyl, C C₄alkylaminocarbonyl or di- (C C₄alkyl)aminocarbonyl; or R₁₄ together with Rn, Rι₂, R13, R15, R₁₇, Rι₈ or R₁9 or, when m is 2, also together with R₁₄ forms a direct bond or a d-C₄alkylene bridge;

R₁₅ is hydrogen, C C₃alkyl or d-C₃haloalkyl;

R₁₆ is hydrogen, d-C₃alkyl, d-C₃haloalkyl, d-C₄alkoxycarbonyl, d-C₄alkylcarbonyl or N,N- di(C₁-C alkyl)aminocarbonyl; or

Q is a group Q₂

wherein

R₂₁ and R₂₂ are hydrogen or Cι-C₄alkyl;

X₂ is hydroxy, O^"M⁺ wherein M⁺ is an alkali metal cation or ammonium cation; halogen, d-C₁₂alkylsulfonyloxy, d-C ₂alkylthio, C C₁₂alkylsulfinyl, Cι-C₁₂alkylsulfonyl, d-C₁₂halo- alkylthio, C C₁₂haloalkylsulfinyl, CrC^haloalkylsulfonyl, CrC₆alkoxy-CrC₆alkylthio, d-C₆- alkoxy-d-C₆alkylsulfinyl, CrC₆alkoxy-CrC₆alkylsulfonyl, C₃-d₂alkenylthio, C₃-d₂alkenyl- sulfinyl, C₃-Cι₂alkenylsulfonyl, C₃-Cι₂alkynylthio, C₃-C ₂alkynylsulfinyl, C₃-C₁₂alkynylsulfonyl, d-C₄alkoxycarbonyl-CrC alkylthio, CrC₄alkoxycarbonyl-d-C alkylsulfinyl, C C₄alkoxy- carbonyl-CrC₄alkylsulfonyl, benzyloxy or phenylcarbonylmethoxy; it being possible for the phenyl-containing groups to be substituted by R_7f;

R_7f is halogen, d-C₃alkyl, d-C₃haloalkyl, hydroxy, d-C₃alkoxy, d-C₃haloalkoxy, cyano or nitro; or

Q is a group Q₃

wherein

R₃₁ is CrCealkyl, CrC₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl;

R₃₂ is hydrogen, CrC₄alkoxycarbonyl, carboxy or a group S(O)_sR₃₃;

R₃₃ is CrC₆alkyl or d-C₃alkylene, which may be substituted by halogen, d-C₃alkoxy,

C₂-C₃alkenyl or by C₂-C₃alkynyl; and s is O, 1 or 2; or

Q is a group Q₄

wherein

R₄ι is d-C₆alkyl, CrC₆haloalkyl, C₃-C₆cycloalkyl or halo-substituted C₃-C₆cycloalkyl; or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I, and b) a synergistically effective amount of one or more compounds selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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 a crop 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 locus 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 said composition at an application rate corresponding to from 1 to 5000 g of total active ingredient per hectare.

5. A selectively herbicidal composition which comprises, as active ingredient, a mixture of a) an amount, effective for herbicide synergism, of a compound of formula I according to claim 1 and one or more compounds selected from pyridafol, dicamba and its salts, procarbazone, benflubutamid, tralkoxydim, mesosulfuron, chlorsulfuron, triasulfuron, flamprop-M, metoxuron, glufosinate, L-glufosinate, fluthiacet, imazamox, imazethapyr, nicosulfuron, primisulfuron-methyl, rimsulfuron, halosulfuron, cloransulam, clomazone, diclosulam, 2,4-D and its salts, florasulam, flumiclorac, bromoxynil, sethoxydim, ioxynil, tepraloxydim, carfentrazone, clethodim, sulfentrazone, imazaquin, sulcotrione, imazapyr, mesotrione, thifensulfuron, isoxaflutole, prosulfuron, isoxachlortole, bentazone, iodosulfuron, prohexadione, diflufenzopyr, flurtamone, butylate, flumioxazin, fentrazamide, benzfendizone, isopropazole, fluazolate, aclonifen, tritosulfuron, cinidon-ethyl, glyphosate and its potassium, isopropylammonium, sodium, trimesium, ammonium and diammonium salts, terbuthylazine, mesotrione + terbuthylazine, paraquat, ketospiradox, aminopyralid, amicarbazone, azafenidin, flufenpyr-ethyl, the compound of formula II

and the compounds clodinafop-propargyl, prosulfocarb, picolinafen, pyraflufen-ethyl, beflubutamid, fenoxaprop-P-ethyl, diclofop-methyl, amidosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, metsulfuron-methyl, sulfosulfuron, tribenuron-methyl, imazamethabenz-methyl, flucarbazone, chlortoluron, isoproturon, methabenzthiazuron, bifenox, fluoroglycofen-ethyl, imazosulfuron, diflufenican, bilanafos, ethalfluralin, fluthiamide, isoxaben, trialiate, 2,4-DB, dichiorprop, 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

the salts or 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 the methyl and ethyl esters 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

and of formula 3.18

and of formula 3.19

6. A method of selectively controlling weeds and grasses in a crop of useful plants, which comprises treating the useful plants, seeds or seedlings 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 herbicides 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 which comprises, as active ingredient, a mixture of a) a herbicidally effective amount of a 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

the salts or 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 the methyl and ethyl esters 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

and of formula 3.18

and of formula 3.19

10. A method of selectively controlling weeds and grasses in a crop of useful plants, which comprises treating the useful plants, seeds or seedlings thereof, or the area of cultivation thereof, with a herbicidally effective amount of a composition according to claim 9.