WO2009007014A1 - Water-soluble concentrates of 3-(2-alkoxy-4-chloro-6-alkylphenyl)-substituted tetramates and their corresponding enols - Google Patents

Abstract

The present invention relates to novel water-soluble concentrates of 3-(2-alkoxy-4-chloro-6-alkylphenyl)-substituted tetramates and their enols, processes for producing these formulations and their use as pesticides and/or herbicides.

Description

 Water-soluble concentrates of 3- (2-alkoxy-4-chloro-6-alkyl-phenyl) -substituted tetramates and their corresponding enols

The present invention relates to novel water-soluble concentrates (SL formulations) of 3- (2-alkoxy-4-chloro-6-alkyl-phenyl) -substituted tetramates and their enols, to processes for preparing these formulations and to their use as herbicides.

Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones are described above (Suzuki, S. et al., Chem. Pharm. Bull, supra, 1120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones were synthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095). Biological activity of these compounds has not been described.

EP-A-0 262 399 and GB-A-2 266 888 disclose similarly structured compounds (3-arylpyrrolidine-2,4-diones), of which, however, no herbicidal, insecticidal or acaricidal action has become known. Unsubstituted, bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053 670 are known to have herbicidal, insecticidal or acaricidal activity and substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077).

Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and 1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334, EP-A- 596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96 / 35,664, WO 97/01 535, WO 97/02 243, WO 97/36868, WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/24437, WO 99/43649 , WO 99/48869 and WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/013249, WO 03/062244, WO 2004/007448, WO 2004/024 688, WO 04 / 065366, WO 04/080962, WO 04/11 1042, WO 05/044791, WO 05/044796, WO 05/048710, WO 05/049596, WO 05/066125, WO 05/092897, WO 06/000355, WO 06 / 029799, WO 06/056281, WO 06/056282, WO 06/089633 and WO 07/048545). In addition, ketalsubstituted 1-H-arylpyrrolidine-2,4-diones from WO 99/16748 and (spiro) - ketalsubstituted N-alkoxy-alkoxy-substituted aryl-pyrrolidindione from JP-A-14 205 984 and Ito M. et. al Bioscience, Biotechnology and Biochemistry 67, 1230-1238, (2003). 3- (2-alkoxy-4-chloro-6-alkyl-phenyl) -substituted tetramic acids are known from WO 2004/080962.

However, the herbicidal activity and / or the range of action and / or the plant tolerance of the known compounds, in particular to crop plants, is not always sufficient.

In WO 04/080962 are as concentrated formulations of the below-mentioned drugs only EC formulations disclosed (Emulsifiable concentrates). These are then diluted in water for use. A concentrated aqueous formulation is not disclosed.

DE 35 13 889, US 6,184,182 and US 5,389,598 disclose the use of certain surfactants in pesticides or herbicidal compositions. But these are other active ingredients than the invention.

It has now been found that concentrated compositions containing a phase containing at least one dissolved active compound of the formulas (I-A) or (I-B)

where in the formulas (IA) and (IB)

X is methoxy or ethoxy,

W is methyl or ethyl,

stands for chlorine,

m is 1, 2 or 3,

n is 1, 2 or 3,

is Cj-C ^ alkyl or cyclopropyl,

B is methyl,

D stands for hydrogen

or

A, B and the carbon atom to which they are attached together for saturated C5-C6-cycloalkyl in which optionally a ring member is replaced by oxygen and which is optionally substituted by methyl, methoxy or ethoxy,

or

A and D together represent a C 1 -C 4 -alkylidenyl group,

G is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent

Aluminum or an ion equivalent of a transition metal is or remains

is an ammonium ion, in which optionally one, two, three or all four hydrogen atoms by identical or different radicals from the groups hydrogen, C 1-C ₅ -alkyl, C ₁ -C ₅ -IsOaIlCyI or C ₃ -C ₇ - Cycloalkyl, which may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms, replaced, or continue

for a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] undecarboxylic acid 7-en (DBU), stands, or continues

for a heterocyclic ammonium cation, for example in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, Pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate, stands or remains

is a sulfonium ion, or continues

represents a magnesium-halogen cation,

when applied after dilution in water to suitable concentrations have a faster onset of action and / or a better crop tolerance and / or a higher efficacy than, for example, corresponding WP or SC formulations in which the active ingredient of the formula (IA) or (IB) is particulate as long as the formulation is not diluted in water. In the formulations according to the invention, the active compounds are already present in dissolved form in the concentrated compositions.

This is particularly surprising because, due to the very high water solubility of the active ingredients, starting from any formulated type, after dilution in water immediate availability - and so that an independence of the effect of the original formulation type - would have been expected.

The present invention accordingly provides compositions comprising at least one solvent and at least one compound of the formula (I-A) or (I-B) in dissolved form.

The present invention also provides processes for the preparation of water-soluble concentrates comprising at least one compound of the formula (I-A) or (I-B).

The present invention further provides the use of compositions comprising a phase comprising at least one compound of the formula (I-A) or (I-B) in dissolved form for controlling undesired plant growth.

In general, all the compounds of the formulas (I-A) or (I-B) listed above can be used in the compositions according to the invention.

Preference is given to using compounds of the formula (I-B) in which G is an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminum or an ion equivalent of a transition metal.

Preference is furthermore given to using compounds of the formula (IB) in which G is an ammonium ion in which optionally one, two, three or all four hydrogen atoms are represented by identical or different radicals from the groups hydrogen, C 1 -C 8 -alkyl, C 1 -C 4 -alkyl ₅ -isoalkyl or C ₃ -C ₇ -cycloalkyl, each of which may be substituted one or more times by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms.

Particular preference is given to using compounds of the formula (I-B) in which G is lithium, sodium, potassium, magnesium, calcium, barium, copper, zinc, aluminum, ammonium, trimethyl or triethylsulfonium.

Very particular preference is given to using compounds of the formula (I-B) in which G is lithium, sodium, potassium, magnesium, calcium or ammonium.

Particularly useful are compounds of formula (I-B) in which G is lithium, sodium, potassium.

In particular, compounds of the formula (I-A) can be used.

Compounds of the formula (IA) which can be used according to the invention are shown in Table 1 shown, wherein each compound contained therein is preferred for itself.

Particularly preferred compounds of the formula (I-B) which can be used according to the invention are shown in Tables 2a and 2b, with each compound contained therein being preferred per se.

H-NMR (300 MHz, D ₂ O): shifts δ in ppm

** ¹ H-NMR (400 MHz, DMSO-d6): shifts δ in ppm

* ¹ H-NMR (300 MHz, D ₂ O): shifts δ in ppm ** ¹ H-NMR (400 MHz, DMSO-d6): shifts δ in ppm

It has also been found (see Examples A and B) that the effect of compositions comprising a phase containing at least one compound of the formulas (I-A) or (I-B) in dissolved form can be increased by the addition of certain surfactants.

Suitable surfactants are, for example, sulfates, sulfonates, phosphates and phosphonates of hydrocarbons, which may optionally contain alkylene oxide units. The sulfates, sulfonates, phosphates and phosphonates may be in the form of the acids or as salts. Anionic surfactants of the following formula (H) are preferred:

R - Q (II)

wherein

Q is -O- SO ₃ M, -SO ₃ M, -0-PO ₃ HM or -PO ₃ HM,

wherein M is hydrogen or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion,

R is an unsubstituted or substituted Ci-C ₃ o-hydrocarbon radical, optionally via

Alkylene oxide units may be bonded, or R is an alkylene oxide unit.

The term alkylene oxide units, in particular units of C ₂ -C _O - alkylene oxides such as ethylene oxide, propylene oxide or butylene understood, the units may be arranged differently and thereby randomly mixed or in blocks within the surfactant same or different.

Preferably, R is a C, -C ₂ o-alkyl radical (eg, methyl, ethyl, propyl, butyl) or a C ₆ -C ₂₄ aryl radical (eg, phenyl, biphenyl, naphthyl), which may optionally carry one or more radicals, for example from the group Ci-C ₂₀ alkyl (for example, linear or branched _Ci-C2o-alkyl such as sec. butyl or dodecyl) which comprises one or more radicals such as C ₆ -C ₂₀ aryl radicals (such as phenyl, biphenyl, naphthyl) and C ₆ -C ₂₀ -aryl (eg phenyl, biphenyl or naphthyl), which may optionally carry one or more radicals such as C _r Ci ₀ alkyl (eg, methyl, ethyl, propyl, butyl), or

R is a radical R'O- (AO) _W , wherein w is an integer from 1 to 100, and AO is an alkylene oxide moiety, eg (EO) _X (PO) _Y (BO) _Z , where EO is an ethylene oxide moiety, PO a propylene oxide unit, BO is a butylene oxide unit, x is an integer from 0-100, y is an integer from 0-100, z is an integer from 0 to 100 and the sum x + y + z is at least 1, and the alkylene oxide unit, eg (EO) _X (PO) _Y (BO) _Z , randomly mixed or block-structured, and R ¹ is H, a C _r C ₂ o-alkyl radical (for example methyl, ethyl, propyl, butyl) or a C ₆ -C ₂₄ -aryl radical (for example phenyl, biphenyl, naphthyl), which may optionally carry one or more radicals, for example, from the group Ci-C ₂ o-alkyl (eg linear or branched Ci-C ₂ o-alkyl such as sec-butyl or dodecyl), which one or more radicals such as Cβ-Qo-aryl radicals (eg, phenyl, biphenyl, naphthyl) and C ₆ -C ₂₀ -alkyl (for example phenyl, biphenyl, naphthyl), which may optionally carry one or more radicals, such as C 1 -C ₁₀ -alkyl (for example methyl, ethyl, propyl, butyl), or R ₂ -O-SO ₃ M, -SO ₃ M, -O-PO ₃ HM, H or -PO ₃ HM, preferably PO ₃ HM, wherein M is H or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or a Ammonium ion is.

Particularly preferred surfactants are alkylaryl sulfonates such as dodecyl benzene sulfonates, e.g. Erdalkalidodecylbenzolsulfonate such as calcium dodecylbenzenesulfonates (eg Phenylsulfonat® CaIOO from Clariant), Alkylarylpolyglykolethersulfate and sulfonates, in particular Arylalkylarylpolyglykolethersulfate as Tristyrylphenolpolyglykolethersulfate, in particular the alkali or ammonium or triethanolamine salts (eg Soprophore® series of Rhodia), alkyl ether sulfates and their salts (eg Genapol® LRO from Clariant), alkyl sulfates and alkyl sulfonates (eg, such as the Hostapur® series from Clariant), alkyl polyglycol ether phosphates, in particular the alkali metal salts (eg the Rhodafac® series Rhodia),

Alkylaryl polyglycol ether phosphates, in particular in the form of the alkali metal salts. The salts are generally preferably metal salts such as alkali or alkaline earth metal salts or ammonium or trialkylamine salts.

Most preferred are alkyl ether sulfates and their salts (e.g., such as Genapol® LRO ex Clariant).

Suitable surfactants are, for example, also alkanol alkoxylates into consideration. Surfactants according to the invention are alkanol alkoxylates of the formula (III)

R ² -O - (- AO) _m -H (m)

in which

R ^{2 is} straight-chain or branched alkyl having 4 to 20 carbon atoms,

AO stands for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and

m stands for numbers from 2 to 20. A preferred group of surfactants are alkanol alkoxylates of the formula (DI-a)

R ² -O - (- EO-) _b -H (ma)

in which

R ^{2 is} branched alkyl having 8 to 15 carbon atoms,

EO stands for -CH ₂ -CH ₂ -O- and

b stands for numbers from 4 to 18.

Also suitable surfactants are cationic surfactants derived from primary fatty alcohol amines. These may e.g. represented by the formula (IV):

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20 carbon atoms and the sum of p and q is 15 to 25.

The above-mentioned surfactants may be present as a mixture of different substances which fall under the general formulas (II), (III) and (FV). In particular, the values given for m, b, p and q are averages.

Particularly preferred surfactants are those of the formula (II).

The present invention accordingly also relates to compositions comprising in addition at least one phase containing at least one compound of the formulas (IA) or (I-B) in dissolved form and at least one surfactant selected from the surfactants of the formulas (II), (DI) and (IV).

Suitable solvents in the compositions according to the invention are all water-miscible solvents conventionally used in agrochemical formulations in which the active compounds of the formulas (IA) and (IB) are dissolved in the concentrations used here. Examples which may be mentioned are water, alcohols such as methanol, ethanol or isopropanol, ethers or polyethers such as 1,4-dioxane, tetrahydrofuran or dimethoxyethane, amides such as formamide, Acetamide, N, N-dimethylformamide, N, N-dimethylacetamide or Hallcomid® (mixture of 50-60% N, N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide), sulfoxides / sulfones such as dimethyl sulfoxide or sulfolane and lactones / Lactams such as N-methylpyrrolidone and gamma-butyrolactone.

Preferred solvents are water, methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran, dimethoxyethane, Hallcomid® (mixture of 50-60% N, N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide), dimethyl sulfoxide, sulfolane , N-methylpyrrolidone and gamma-butyrolactone.

Particularly preferred as the solvent is water.

For the preparation of the water-soluble concentrates of the invention containing a compound of formula (IB), it is advantageous to generate the compound of formula (IB) in situ during the preparation of the composition by reacting the corresponding compound of formula (IA) with a suitable base ,

This process enables the preparation of compositions containing compounds of formula (I-B) which are less stable in isolated form. Suitable bases are in principle all organic and inorganic bases, as far as their use is harmless for agricultural purposes.

Examples of bases are

a) metal hydroxides such as lithium, sodium and potassium hydroxide, magnesium and calcium hydroxide, aluminum hydroxide, zinc hydroxide or

copper hydroxide,

b) metal oxides such as lithium, sodium and potassium oxide or alumina

c) amines of the general formula NR ¹ R ² R ³ . In it, R ¹ , R ² and R ^{3 may be the} same or different and each represents hydrogen, CpCs-alkyl, Ci-C ₅ -isoalkyl or C ₃ - C ₇ -cycloalkyl, which in turn in each case one or more times with fluorine, chlorine , Bromine, cyano,

Hydroxy substituted or interrupted by one or more oxygen or sulfur atoms.

Specific examples are ammonia, methylamine, dimethylamine, triethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, ethanolamine, diethanolamine, triethanolamine, 2-diethylaminoethanol, diisopropylamine, cyclohexylamine, dicyclohexylamine, d) mono-, bi- or tricyclic amines such as, for example, morpholine, thiomorpholine, piperidine, pyrrolidine, 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] un-decane 7-en (DBU),

e) diamines such as N, N-bis (2-hydroxyethyl) -C ₈ -C ₈ -alkylamines, lentetramin hexamethylene, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, 2 Diethylaminoethylamine, NNN'.N'-tetraethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, 2- (2-aminoethylamino) ethanol or lysine,

f) aromatic amines such as pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, Pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate,

g) carbonates, such as, for example, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, magnesium carbonate, calcium carbonate, copper carbonate, zinc carbonate or lithium carbonate,

h) sulphites, such as, for example, sodium, potassium, lithium or zinc sulphite,

i) phosphates such as lithium potassium, sodium, calcium and magnesium phosphate, lithium, potassium, sodium, calcium and magnesium hydrogen phosphate or potassium and sodium dihydrogen phosphate,

j) alcoholates such as, for example, sodium and potassium methylate or ethylate,

k) ammonium hydroxides, such as, for example, trimethyl, triethyl, tripropyl or tributylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetraethanolammonium hydroxide or methyltriethylammonium hydroxide,

1) amidines and guanidines, each of which may optionally be substituted, for example acetamidine, formamidine, guanidine, 1,1,3,3-tetraaminoguanides, aminoguanidine or arginine,

m) basic carboxylic acid salts, preferably acetates such as lithium, sodium or potassium acetate, oxalates such as sodium or potassium oxalate, tartrates such as sodium or potassium tartrate, and citrates such as sodium or potassium citrate,

n) strongly or weakly basic anion exchangers loaded with hydroxide ions, for example, those commercially available under the names AMBERLITE®, AMBERLYST®, DUOLITE®, DOWEX® or LEWATITE®.

The base can in principle also be used in immobilized form, it being possible for the carrier material to be separated off after preparation of the concentrate according to the invention, for example by filtration.

Depending on the need, based on the amount of the compounds of the general formula (I-A) used, between 0.1 and 100 molar equivalents, typically 0.5 to 3 molar equivalents, of the base can be used.

Preferred as basic auxiliaries are lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and ammonia, alkylamines and hydroxyalkylamines.

Optionally, the formulations according to the invention contain further additives from the groups of the foam-inhibiting agents, the antioxidants and / or the dyes.

Suitable foam-inhibiting substances are all substances customarily usable for this purpose in agrochemical compositions. Preference is given to polydimethylsiloxanes, silicone oils and magnesium stearate.

As antioxidants are all commonly used for this purpose in agrochemical agents substances into consideration. Preference is given to butylhydroxytoluene (2,6-di-t-butyl-4-methylphenol, BHT).

Suitable dyes are all substances customarily usable for this purpose in agrochemical compositions. Examples include titanium dioxide, carbon black, zinc oxide and blue pigments as well as permanent red FGR.

In the formulations according to the invention which contain as active herbicidal agents only active compounds of the formula (IA) or (IB), the content of active compound of the formula (IA) or (IB) is generally from 0.1 to 50% by weight, preferably 0 , 2 to 50 wt .-%, particularly preferably 1 to 25 wt .-%, most preferably 2 to 20 wt .-%.

In the formulations according to the invention, the content of surfactant (active substance, possibly corrected by water content) is generally from 5 to 50% by weight and preferably from 10 to 30% by weight.

In ready-to-use formulations (spray liquors), the content of surfactant is generally 0.1 to 10 g / l, preferably 0.3 to 3 g / l. The surfactant is generally applied at a rate of from 20 to 1000 g ai / ha, preferably from 100 to 300 g ai / ha.

Compositions according to the invention may additionally comprise, in addition to at least one compound of the formula (IA) or (IB), at least one further herbicidal active ingredient, preferably from the group consisting of acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (- sodium), ametryne, Amicarbazone, amidochlor, amidosulfuron, aminopyralid, anilofos, asulam, atrazine, azafenidine, azimsulfuron, beflubutamide, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, bencarbazone, benzfendizone, benzobicyclone, benzofenap, benzoylprop (-ethyl ), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxime, Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylate, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron ( ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidone (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, Clopyra-sulfurone (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclo-sulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, dialkylates, Dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethylamine, dinitramine, diphenamid, diquat, dithiopyr, Diuron, Dymron, Epropodan, EPTC, Espr-carb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanide, Fenoxaprop (-P-ethyl), Fentrazamide, Flamprop (-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (p-butyl), fluazolates, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (pentyl), flumioxazine, flumipropyne, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), Flupoxam, flupropacil, fluφyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypro pyl, meptyl), flurprimidol, flur-tamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), L-glufosinate (-sodium, -ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, -P-methyl), hexazinone, HOK-201, imazamethabenz-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, Isourone, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfurones, mesotrione, metamifop, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha) metolachlor, metosulam, metoxuron, Metribuzin, metsulfuron (-methyl), molinates, monolinuron, naproanilides, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazone, oxasulfuron, oxaziclomefones, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendraline, Pe noxsulam, pentoxazone, phenmedipham, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulphixron (-methyl), Profluazole, Prometry, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrasulfotole, Pyrazogyl, Pyrazolate, Pyrazosulphuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyridatol, pyrif- idalid, pyrimino-bac (-methyl), pyrimisulfane, pyrithiobac (-sodium), pyroxasulfones, pyroxsulam, quinchlorac, quinmerac, quinoclamine, quizalofop (-P -ethyl, -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tembotrione, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin , Thifensulfuron (-methyl), thiobencarb, tiocarbazil, toramezone, tralkoxydim, triallates, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulruron, triflusulfuron (-methyl), tri tosulfuron and the following six compounds

Compositions of the invention may also contain herbicidal safeners. Examples of such safeners are Benoxacor, Cloquintocet-mexyl, Cumyluron, Dymron, Dimepiperate, Cyprosulfamide, Cyometrinil, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Fenchlorazolethyl, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen, Isoxadifen-ethyl, Mefenpyr, Mefenpyr diethyl, mephenate, naphthalic anhydride, oxabetrinil

Preferred safeners are mefenpyr-diethyl and isoxadifen-ethyl

Preference is given according to the invention to compositions comprising as herbicidal active substances

- A.3 and glyphosate

- B.6 and glyphosate

- A.3 and glufosinate

- B.6 and glufosinate

- A.3 and L-glufosinate

B.6 and L-glufosinate

A.3 and fenoxaprop-P-ethyl

B.6 and fenoxaprop-P-ethyl.

Preferred compositions according to the invention are also those comprising at least one compound of the formulas (IA) or (IB), fenoxaprop-P-ethyl and mefenpyr-diethyl and compositions containing at least one compound of the formulas (IA) or (IB), fenoxaprop-P-ethyl and isoxadifen-ethyl.

In the formulations according to the invention which contain as herbicidal active ingredients both at least one active substance of the formulas (IA) or (IB) and at least one further active ingredient and optionally a safener, the total content of active substances and optionally safeners generally 0.2 to 50 wt .-%, preferably 1 to 40 wt .-%, particularly preferably 2 to 30 wt .-%.

If the additionally present herbicidal active ingredient in the solvent used for the active ingredient of the formula (I-A) or (I-B) is soluble in the required concentrations, all active ingredients can be dissolved in one phase. The concentrates of the invention are then (e.g., water-based) soluble concentrates.

The invention accordingly provides compositions containing

a phase comprising at least one dissolved active compound of the formulas (I-A) and (I-B) and a further active substance selected from glyphosate, glufosinate or L-glufosinate,

optionally further additives from the groups of the foam-inhibiting agents, the antioxidants and / or the dyes and

at least one solvent.

The invention therefore particularly preferably contains compositions

a phase containing at least one dissolved active substance selected from A2, A.3, B4 and B6 and a further active substance selected from glyphosate, glufosinate or L-

glufosinate,

optionally further additives from the groups of the foam-inhibiting agents, the antioxidants and / or the dyes and

at least one solvent.

Surprisingly, it has also been found that such compositions, if they already contain both active ingredients in concentrated form, are more effective than mixtures of identical active ingredients produced by tank mix at the same application rates. Due to the high water solubility of the active ingredients, a dependency on the original type of formulation was not to be expected here as well.

If the further herbicidal active ingredient (such as fenoxaprop-P-ethyl) is not soluble in the solvents used for (IA) or (IB), then the further active ingredient can be dissolved in another suitable solvent. The two phases can then be mixed, resulting, for example, in an EW formulation (emulsion in water). The invention accordingly provides compositions containing

a phase comprising at least one dissolved active compound of the formulas (I-A) or (I-B),

another phase containing at least one further dissolved or particulate active ingredient,

- Optional other additives from the groups of emulsifiers, foam-inhibiting

Agents of antioxidants and / or dyes.

Preference is therefore given to containing compositions

a phase comprising at least one dissolved active compound of the formulas (I-A) or (I-B),

another phase containing fenoxaprop-P-ethyl,

- Optional other additives from the groups of emulsifiers, foam-inhibiting

Agents of antioxidants and / or dyes.

Accordingly, particular preference is given to containing compositions

a phase containing at least one dissolved active substance selected from A2, A.3, B4 and B6,

a further phase containing fenoxaprop-P-ethyl and mefenpyr-diethyl or

Fenoxaprop-P-ethyl and isoxadifen-ethyl,

optionally further additives from the groups of emulsifiers, antifoaming agents, antioxidants and / or dyes.

Suitable emulsifiers are all customary nonionic, anionic, cationic and zwitterionic substances having surface-active properties which are customarily used in agrochemical compositions. These substances include reaction products of fatty acids, fatty acid esters, fatty alcohols, fatty amines, alkylphenols or alkylarylphenols with ethylene oxide and / or propylene oxide and / or butylene oxide, and their sulfuric acid esters, phosphoric monoesters and phosphoric diesters, also reaction products of ethylene oxide with propylene oxide , furthermore alkyl sulfonates, alkyl sulfates, aryl sulfates, tetra-alkyl ammonium halides, trialkylaryl ammonium halides and alkylamine sulfonates. The emulsifiers can be used individually or in a mixture. Preferably mentioned are reaction products of castor oil with ethylene oxide in a molar ratio of 1:20 to 1:60, Reaction products of C ₆ -C ₂ o-alcohols with ethylene oxide in a molar ratio of 1: 5 to 1: 50, reaction products of fatty amines with ethylene oxide in a molar ratio of 1: 2 to 1: 25, reaction products of 1 mole of phenol with 2 to 3 moles of styrene and 10 to 50 mol of ethylene oxide, reaction products of C 1 -C 4 -alkylphenols with ethylene oxide in a molar ratio of 1: 5 to 1: 30, alkyl glycosides, C 7 -C 12 -alkylbenzene-sulfonic acid salts, such as, for example, calcium, monoethanolammonium, diethanolammonium and triethanolammonium salts. salts.

Examples of nonionic emulsifiers which are known under the names sapogenate T180 (= tri-sec-butylphenol ethoxylate, Clariant Fa), Alkamuls OR36 (= castor oil ethoxylate, Fa Rhodia) and Emulsogen TS54 (= tristyryl phenol ethoxylate, Clariant) Called products. These tristyrylphenol ethoxylates (Emulsogen TS540) are preferably used in the formulations according to the invention. Examples of anionic emulsifiers which may be mentioned under the name Baykanol SL (= condensation product of sulfonated ditolyl ether with formaldehyde) commercially available product of Bayer AG and phosphated or sulfated tristyryl-phenol ethoxylates, Soprophor FLK and Soprophor 4D 384 (Rhodia ) are specifically mentioned.

The compositions according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. It does not matter whether the substances are applied in the pre-sowing, pre-emergence or postemergence process.

Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be named, which can be controlled by the compositions according to the invention, without any restriction being made to certain species by the mention.

On the side of the monocotyledonous grass species, volunteer crops such as wheat, barley, rye and triticale as well as e.g. Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and Bromus spp. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperusarten from the annuelle group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten well.

For dicotyledonous weed species, the spectrum of activity extends to species such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp. , Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., Paphaver rhoeas spp., Centaurea spp. on the annals page as well as Convolvulus, Cirsium, Rumex and Artemisia spp. at the perennial weeds.

If the compositions according to the invention are applied to the surface of the earth before germination, either the weed seedlings are completely prevented or the weeds grow up to the cotyledon stage, but then stop their growth and finally die off completely after three to four weeks.

Upon application of the compositions to the green plant parts postemergence, a drastic growth arrest also occurs very rapidly after the treatment and the weed plants remain in the growth stage existing at the time of application or die completely after a certain time, so that in this way one for the crop plants harmful weed competition is eliminated very early and sustainably.

The herbicidal compositions of the invention are characterized by a rapidly onset and long-lasting herbicidal activity. The rainfastness of the active ingredients in the compositions according to the invention is generally favorable. By means of the compositions according to the invention, a considerable reduction in the required application rate of the active ingredients is made possible.

The compositions according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants, including species which are resistant to herbicidal active substances such as glyphosate, glufosinate, atrazine or imidazolinone herbicides.

Although the compositions according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous harmful plants, the crop plants are damaged only insignificantly or not at all.

Moreover, some of the compositions of the invention have excellent growth-regulatory properties in the crop plants. They regulate the plant's metabolism and can thus be used to influence the metabolism

Phytochemicals and to facilitate harvesting, e.g. by triggering desiccation and

Stunted growth can be used. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, as crop losses during storage can be reduced or completely prevented. Because of their herbicidal and plant growth-regulating properties, the compositions according to the invention can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known. Other special properties may be in a tolerance or resistance to abiotic stressors z. As heat, cold, drought, salt and ultraviolet radiation.

Preference is given to the use of the compositions according to the invention comprising compounds of the formula (I-A) or (I-B) in economically important transgenic crops of useful and ornamental plants, for. As cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or cultures of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables.

Preferably, compositions containing compounds of the formula (I-A) or (I-B) can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.

Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by means of genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described

genetically engineered crop modifications to modify the starch synthesized in the plants (eg WO 92/11376, WO 92/14827, WO 91/19806),

transgenic crop plants which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0242236, EP 242246) or glyphosate (WO 92/00377) or the

Sulfonylureas (EP 0257993, US 5013659) are resistant,

transgenic crops, for example cotton, having the ability Bacillus to produce thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP 0142924, EP 0193259).

Transgenic crop plants with modified fatty acid composition (WO 91/13972).

genetically modified crops with new content or secondary substances z. B. new phytoalexins that cause increased disease resistance (EP 309862, EP

0464461)

genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EP 0305398).

Transgenic crop plants that produce pharmaceutically or diagnostically important proteins ("molecular pharming")

Transgenic crops that are characterized by higher yields or better quality

transgenic crops characterized by a combination z. B. the o. G. characterize new properties ("gene stacking")

Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in principle; see, for. B. I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431).

For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. With the help of standard methods z. For example, base substitutions are made, partial sequences are removed, or natural or synthetic sequences are added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see, for example, US Pat. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. CoId Spring Harbor Laboratory Press, ColD Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996

The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect, or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product. For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.

In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z. For example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The expression of the nucleic acid molecules can also take place in the organelles of the plant cells.

The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.

Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.

Preferably, the compounds or compositions according to the invention can be used in transgenic cultures which are resistant to growth substances, such. B. 2,4-D, dicamba or herbicides, the essential plant enzymes, eg. As acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or Hydoxyphenylpyruvat dioxygenases (HPPD) inhibit or herbicides from the group of sulfonylureas, glyphosate, glufosinates or benzoylisoxazoles and analogues, or resistant to any combination of these agents. An example of this are transgenic crops such. B. corn or soybean with the trade name or designation Optimum ™ GAT ™ (Glyphosate ALS Tolerant)

With very particular preference the compounds or compositions according to the invention can also be used in transgenic crop plants which are resistant to glufosinates, L-glufosinates or glyphosates or a combination of glufosinates or L-glufosinates and glyphosates. In the application of the active compounds according to the invention in transgenic crops, in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.

The invention therefore also relates to the use of the compositions according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The invention also relates to the use of the compositions for controlling harmful plants, preferably in plant crops.

The herbicidal compositions according to the invention can also be employed non-selectively for controlling unwanted plant growth, for example in plantation crops, on roadsides, squares, industrial plants or railway installations.

Preparation Examples

Preparation of water-dispersible powders (WP formulations)

The active ingredient was mixed with inert material. The powder was ground until an average particle size (d50) of 5 to 10 μm was reached.

A typical composition of a WP20 formulation was:

A.3 20% by weight

Sipernat® 22S 10% by weight

Baykanol® SL 10% by weight

Galoryl® MT 804 4% by weight

Kaolin W 54% by weight

Preparation of suspension concentrates (SC formulations)

The active ingredient was stirred into an aqueous solution of a suitable surfactant. The dispersion was finely ground using standard equipment until an average particle size of less than 5 microns was achieved. A typical composition of an SCl 50 formulation was:

A.3 150 g / l

1,2-propylene glycol 52 g / l

Agnique® PG 8105 G 31 g / l

Arkopon® T 21 g / l

Acticide® MBS 2 g / l

Rhodopol® 23 2 g / l

Water 773 g / l Production of water-soluble concentrates (SL formulations)

The SL formulation was prepared by stirring and dissolving the active ingredient in water. The solutions contained up to 4 g / l active ingredient of the formula (I-A) or up to 100 g / l active ingredient of the formula (I-B). Additionally, to increase biological activity, optionally water-soluble surfactants up to a level of 300 g a.i. / 1 (a.i. = active ingredient) was added.

Aqueous solutions of the Li, Na and K salts of the active ingredient can also be prepared by simultaneous stirring of active ingredient (I-A) and an equimolar amount, for example, of LiOH, NaOH or KOH or the corresponding carbonates, acetates or phosphates.

A typical composition of an SL formulation was:

B.6 1 1 g / l

Genapol® LRO fluid 764 g / l (28% solution in water)

Rhodorsil® 481 3 g / l

Water 254 g / l

Similarly, in this example, the salts according to the invention B.10 or B.14, B.18 or B .23 could be used

Preparation of compositions containing several herbicidal active substances

Compositions according to the invention may contain, in addition to at least one active compound of the formulas (IA) and (IB), further herbicidal active compounds or further active compounds and herbicidal safeners. These coformulations are prepared by mixing the individual components. Instead of the salt (IB) it is also possible to use a mixture of (IA) and, for example, sodium hydroxide, sodium carbonate, sodium methoxide, sodium acetate, sodium oxalate, sodium oxide or sodium phosphate. Alternatively, a mixture of (I-A) and, for example, potassium or lithium hydroxide, potassium or lithium carbonate, potassium or lithium ethoxide, sodium, potassium or lithium, potassium or lithium acetate, potassium or lithium oxalate, potassium or lithium oxide or potassium or lithium phosphate. The preparation of the EW formulations may require the use of higher shear forces to adequately disperse the organic phase in the aqueous solution. Suitable for this purpose are the known devices, such as tooth colloid mills. Also, incorporation of (IA) or (IB) (or (IA) in combination with the basic excipients exemplified above) into finished commercial products such as Puma Super, Ralon, Ricestar, Whip, Basta / Liberty, Reyy, Finale or Ignite is possible in the manner described. Examples of such formulations are listed below:

Mixture example 1 (SL formulation)

A.3 0.25% (= 2.8 g / L)

Glufosinate-ammonium 13.47% (= 150 g / L)

Genapol® LRO paste 58.62%

1-methoxy-2-propanol 9.97%

Rhodorsil® Antifoam 0.25%

Duasyn acid blue AE 02 0.005%

Water ad 100%

Mixture example 2 (SL formulation)

B.6 0.54% (= 6.25 g / L)

Glufosinate-ammonium 24.50% (= 280 g / L)

Agnique® PG 8105 9.2%

Tetrahydrofurfuryl alcohol 6.2%

Break-Thru® S 200 0.6%

SAG 1572 0.05%

D & C Red 33 0.003% Agnique® SLES 270 35.15%

Water ad 100%

Mixture example 3 (EW formulation)

B.6 0.74% (= 7.8 g / L)

Mefenpyr diethyl 7.12% (= 75 g / L)

Fenoxaprop-P-ethyl 6,55% (= 69 g / L)

Genapol® X-060 15.20%

Glycerine 9.98%

Dispergator® V 4133 Na salt, 20% 9.48%

Emulsogen® EL 400 1, 00%

Mergal® K9N 0.20%

Sodium hydroxide 0.01%

Water 14.81%

Solvesso® 200 ND ad 100%

Analogously, in the above mixing examples 2 and 3, the salts B.10. B.14, B.18 or B.23 in the appropriate quantity.

Mixture example 4

Glyphosate isopropylammonium 28, .62% (= 337 g / L, equivalent to 250 g / L glyphosate)

B.6 0.29% (= 3.5 g / L)

Sodium hydroxide platelets 3.65%

Terwet l250 10.77% Water ad 100%

Preparation of spray mixtures

It was submitted a water application rate of 300 l / ha. Subsequently, the finished formulation was added in the required amount. The spray mixture thus obtained was homogenized by stirring. Alternatively, the spray mixture can also be prepared by "tank mixing" of the individual constituents, for example by successively stirring in a commercial glufosinate, glyphosate or fenoxaprop-P-ethyl-containing product and a formulation of the active ingredient (IA) or (IB). whether in the form of WP, SC, SL, EW or WG.

Biological experiments

Used abbreviations:

g a.i./ha = grams of active ingredient / hectare

l / ha = liter / hectare

ALOMY = Alopecurus myosuroides

APESV = Apera spica venti

AVEFA = Avena fatua

BROER = Bromus erectus

LOLMU = Lolium multiflorum

SETLU = Setaria lutescens

SETVI = Setaria viridis

ECHCG = Echinochloa crus galli

PHACA = Phalaris canariensis

CYNDA = Cynodon dactylon

TRZAS = Triticum aestivum

HORVS = Hordeum vulgar

ZEAMD = Zea mays

General method for the determination of herbicidal activity

For climatic chamber experiments plant seeds were sown at a depth of 1 cm and cultivated in a climatic chamber (12 h light, temperature day: 18 ° C, night: 14 ° C) until the growth stage BBCH 12 to BBCH 13.

The plants were treated on a laboratory spray track with the appropriate spray liquors. The amount of water used for the spray application was 300 l / ha. After treatment, the plants were placed back in the climatic chamber.

For field trials, the test plants were sown in the field and grown to the desired application stage. The spray mixtures were applied with a post-emergence spray bar. The amount of water used was 2001 / ha.

The assessment of the climatic chamber and field trials was carried out after the specified time according to a scale from 0 to 100%:

0% no discernable effect compared to untreated plants

100% killed all plants.

Example A

For a climate chamber test, SC formulations of active ingredient A.3 were prepared as indicated above and used after dilution at a dose of 10 g / ha. 21 days after the application, the efficacy against weeds was evaluated. The results in Table A clearly show the good increase in activity by surfactants according to the invention such as Genapol® LRO, Genapol® Xl 50 and Genamin® T200NF.

Example B

For this climate chamber test, spray mixtures were prepared starting from WP 20 formulations of the active compound A.3, to which ammonium sulfate was added at a rate of 500 g / ha. 21 days after the application, the efficacy against the weeds was evaluated.

The evaluations gave the results listed in Table B, which clearly show the good efficacy of the herbicide in combination with wetting agents such as Genapol® LRO, Genapol® X 150 and Genamin® T200NF.

Table A

4

O

All effects are in%

Table B

* 500g / ha ammonium sulfate was added to all the spray liquors

All effects are in%

Example C

For this climatic chamber test, the spray mixtures used were prepared from an SC formulation with the active ingredient A.3 or an SL formulation of the corresponding sodium salt (B.6) analogously to the preparation examples. In addition, 500 g / ha of ammonium sulfate and 1 l / ha of Genapol LRO were added to the spray mixtures in liquid form.

17 and 31 days after the application, the efficacy against the weeds was evaluated. The results in Table C demonstrate the much earlier onset of action and the overall higher efficacy of SL formulations over SC formulations.

Example D

For this climate chamber test, the spray mixtures used were prepared from a WP formulation with the particular active compound of the formula (I-A) or an SL formulation of the corresponding sodium salt of the formula (I-B) analogously to the preparation examples. In addition, 500 g / ha of ammonium sulfate and 1 l / ha of Genapol LRO were added to the spray mixtures in liquid form.

21 days after the application the efficacy was evaluated. The results in Tables D1 to D3 demonstrate the faster and better efficacy of the SL formulations compared to the WP formulations.

Table C

DAA = Days after application = days after treatment

W

Table D1

* 1 liter / hectare of Genapol LRO liquid and 500 g / hectare of ammonium sulfate were added to each spray mixture.

Table D 2

Table D 3

Example E 1

For this climatic chamber test, the spray liquors from the commercially available product Liberty® (SL formulation, Bayer CropScience) or a ready-to-use formulation according to mixture example 1 were prepared by dilution with water to the concentration indicated in table El.

The efficacy was assessed 10 and 21 days after application. Table E 1 shows the clear superiority of the A.3-containing SL-finished formulation compared to the pure Liberty® product.

Table E 1

DAA = Days after application = days after treatment

Example E 2

For this climate chamber test, the following spray liquors were prepared by diluting the formulations with water and applied at the application rates indicated in Table E2:

- Commercially available product Liberty® (SL formulation, Bayer CropScience) plus active ingredient A.3 as WP 20% (tank mix method)

- SL-finished formulation containing 140 g / L glufosinate-ammonium and 1.4 g of the active ingredient A.3, prepared analogously to mixture Example 1 The effectiveness was assessed 24 days after application, Table E 2 shows the clear superiority of the SL-finished formulation compared to the WP tank mix in the control of Avena fatua and volunteer crops.

Table E 2

Example E 3

For a field trial, spray liquors were prepared by diluting the appropriate formulations (commercially available Liberty® and Mixing Example 2) with water to the concentrations indicated in Table E33. The application was carried out by spraying on the plants AVEFA (Avena fatua), HORVS (Hordeum vulgare) and ZEAMD (Zea mays). The ZEAMD used is a glufosinate-tolerant variety.

The evaluation was made 42 days after the application according to a scale of 0 to 100%:

0% no discernable effect compared to untreated plants

100% killed all plants.

Table E 3

DAA = Days after application = days after treatment

The result clearly shows the higher efficacy of the B.sup.6-containing glufosinate-ammonium SL formulation compared to the SL-formulation containing glufosinate-ammonium alone. By using B.6 glufosinate-tolerant corn is well controlled. This is beneficial in controlling failed corn.

Example E 4

For another field trial, spray liquors were thinned by diluting the following Prepared formulations with water to the concentrations indicated in Table E 4:

SL ready-to-use formulation containing 154 g / l glufosinate ammonium and 2.66 g / L active ingredient B.6 prepared analogously to mixture example 1

- Tank mix of commercially available Liberty® SL 150 g / L glufosinate ammonium and an SL formulation of the active ingredient B.6 as SL.

The application was carried out by spraying on the plants AVEFA (Avena fatua), ECHCG (Echinochloa crus galli), LOLMU (Lolium multiflorum), PHACA (Phalaris canariensis) and SETVI (Setaria viridis).

The evaluation was made 33 days after the application according to a scale of 0 to 100%:

0% no discernable effect compared to untreated plants

100% killed all plants.

Table E4 shows the superiority of the ready-to-use formulation in controlling the weeds used.

Table E 4

DAA = Days after application = days after treatment Example F

For this climate chamber test, the spray liquors were prepared from a commercially available formulation (EW formulation, Puma®, Bayer CropScience) by dilution to the desired concentration and subsequent addition of the stated amount of active compound of the formula (IA) or (IB) (Tank-M ix - procedure).

The efficacy was assessed 33 days after application. The result shows the significantly higher effectiveness of the spray liquors containing A.3 in comparison to the sprays containing exclusively fenoxyprop-P-ethyl.

Table F

Example G

For a field trial, the spray liquors were prepared from a commercially available formulation (Roundup Ultra®, Monsanto) or the formulation according to Mixing Example 4 by dilution with water to the desired concentration (Table G)

The evaluation of the efficacy was carried out 21 days after the application according to a scale of 0 to 100%:

0% no discernable effect compared to untreated plants

100% killed all plants.

The result in Table G shows the significantly higher effectiveness of the A.3-containing formulation compared to Roundup Ultra®.

Table G

DAA = Days after application = days after treatment

Claims

claims

1. Containing composition

a phase comprising at least one dissolved active compound of the formulas (I-A) or (I-B)

(I-A) (I-B)

wherein in the formulas (I-A) and (I-B)

X is methoxy or ethoxy,

W is methyl or ethyl,

stands for chlorine,

m is 1, 2 or 3,

is 1, 2 or 3,

is Cj-C4-alkyl or cyclopropyl,

B is methyl,

D stands for hydrogen

or

A, B and the carbon atom to which they are attached together represent saturated C 5 -C 6 -cycloalkyl in which optionally one ring member is replaced by oxygen and which is optionally monosubstituted by methyl, methoxy or ethoxy,

or A and D together represent a C 3 -C 4 -alkylidenyl group,

G is an alkali metal ion, an ion equivalent of an alkaline earth metal

An ion equivalent of aluminum or an ion equivalent of a transition metal is or remains

is an ammonium ion in which optionally one, two, three or all four

Hydrogen atoms by identical or different radicals from the groups hydrogen, Ci-C ₅ -alkyl, Ci-C ₅ -ssoalkyl or C ₃ -C ₇ -cycloalkyl, each substituted one or more times with fluorine, chlorine, bromine, cyano, hydroxy or may be interrupted by one or more oxygen or sulfur atoms, are replaced, or continue

for a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo [2.2.2] octane (DABCO) or 1,5-diazabicyclo [4.3.0] undecarboxylic acid 7-en (DBU), stands, or continues

for a heterocyclic ammonium cation, for example each protonated

Pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, pyrrole, imidazole, quinoline, quinoxaline, 1, 2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate, is, or continues

is a sulfonium ion, or continues

represents a magnesium-halogen cation,

at least one solvent.

2. Composition according to claim 1, further containing at least one surfactant.

3. Composition according to claim 2, comprising

0.1 to 50% by weight of active compound of the formula (I-A) and / or of the formula (I-B)

5 to 50% by weight of surfactant water

4. Composition according to claim 2 or 3, characterized in that the surfactant is selected from

Surfactants of the formula (II):

R - Q (II)

wherein

Q is -O-SO ₃ M, -SO ₃ M, -O-PO ₃ HM or -PO ₃ HM,

wherein M is H or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion,

R is an unsubstituted or substituted C ₁ -C 30 -hydrocarbon radical which may optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit,

Alkanol alkoxylates of the formula (ITT)

R ² -O - (- AO) _m -H (π i)

in which

R ^{2 is} straight-chain or branched alkyl having 4 to 20 carbon atoms,

AO for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or

Butylene oxide radicals are and

m stands for numbers from 2 to 20 and

Fatty alcohol amines of the formula (FV)

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20 carbon atoms and

the sum of p and q is 15 to 25.

5. A composition according to claim 1, containing a surfactant of the formula (II) according to claim 4.

6. A composition according to any one of claims 1 to 5, containing as active ingredients at least one compound selected from

A composition according to any one of claims 1 to 6, containing at least one active agent selected from fenoxyprop-P-ethyl, glyphosate, L-glufosinate and glufosinate.

A composition according to any one of claims 1 to 7, comprising

a phase comprising at least one dissolved active substance of the formulas (I-A) or (I-B) and a further active ingredient selected from glyphosate, L-glufosinate and glufosinate,

optionally further additives from the groups of the foam-inhibiting agents, the antioxidants and / or the dyes and

at least one solvent.

A composition according to any one of claims 1 to 8, comprising

a phase comprising at least one dissolved active compound of the formulas (I-A) and (I-B),

another phase containing at least one further dissolved or particulate active ingredient,

- Optional other additives from the groups of emulsifiers, foam inhibitors, antioxidants and / or dyes.

10. A method for controlling undesired plant growth, characterized in that a herbicidally effective amount of a composition according to any one of claims 1 to 9 is applied to harmful plants and / or their habitat.

11. Use of a surfactant selected from surfactants of the formulas (II), (III) or (IV) according to claim 4 for increasing the action of a plant protection agent comprising at least one active compound of the formulas (I-A) or (I-B) according to claim 1.

12. Use according to claim 11, characterized in that at least one surfactant of a concentrated formulation containing at least one active substance of the formulas (I- A) or (IB) according to claim 1 is added.

13. Use according to claim 1 1, characterized in that at least one surfactant of a ready-to-use formulation (spray mixture) containing at least one active compound of the formulas (I-A) or (I-B) is added according to claim 1.

14. A process for the preparation of a composition according to claim 1 comprising at least one compound of formula (I-B) according to claim 1, characterized in that a compound of formula (I-A), a suitable base and all other required components of the composition of a water-miscible

Solvent or water are added.

15. The method according to claim 14, characterized in that in any order a compound of formula (I-A), at least one compound selected from glyphosate, glufosinate and L-glufosinate and other required components are dissolved in a water-miscible solvent or water and to any

Time ammonia is passed through the solution.

16. The composition according to claim 1 in the form of a water-soluble concentrate containing

at least one solvent selected from water, methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran, dimethoxyethane, Hallcomid® (mixture of 50-60% N.N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide),

Dimethylsulfoxide, sulfolane, N-methylpyrrolidone and gamma-butyrolactone and

From 0.2 to 50% by weight of at least one active ingredient dissolved in the above solvent

Formulas (I-A) or (I-B),

5 to 50 wt .-% of at least one surfactant selected from

a) surfactants of the formula (II): R - Q (H)

embedded image in which

Q -0-SO ₃ M, -SO ₃ M, -0-PO ₃ HM or -PO ₃ HM,

wherein M is hydrogen or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or a

ammonium ion,

R is an unsubstituted or substituted C ₁ -C 30 -hydrocarbon radical which may optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit,

b) alkanol alkoxylates of the formula (HT)

R ² -O - (- AO) _m -H (HI)

in which

R ^{2 is} straight-chain or branched alkyl having 4 to 20 carbon atoms,

AO for an ethylene oxide radical, a propylene oxide radical, a

Butylene oxide radical or for mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and

m stands for numbers from 2 to 20 and

c) fatty alcohol amines of the formula (IV)

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20 carbon atoms and

the sum of p and q is 15 to 25.

17. The composition of claim 16, wherein the solvent is water.

18. A composition according to any one of claims 16 or 17, containing as active ingredients at least one compound selected from

19. The composition according to claim 1 in the form of a water-soluble concentrate containing

at least one solvent selected from water, methanol, ethanol, isopropanol,

1, 4-dioxane, tetrahydrofuran, dimethoxyethane, Hallcomid® (mixture of 50-60% N, N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide), Dimethylsulfoxide, sulfolane, N-methylpyrrolidone and gamma-butyrolactone,

at least one active ingredient of the formulas (I-A) or (I-B) dissolved in the above solvent,

at least one active substance also dissolved in the above solvent selected from glyphosate, glufosinate or L-glufosinate,

wherein the herbicidal active ingredients are present in total in an amount of 0.2 to 50 wt .-%,

5 to 50 wt .-% of at least one surfactant selected from

a) surfactants of the formula (H):

R - Q (II)

wherein

Q -0-SO ₃ M, -SO ₃ M, -0-PO ₃ HM or -PO ₃ HM,

wherein M is hydrogen or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion,

R is an unsubstituted or substituted C 1 -C ₃₀ -hydrocarbon radical which may optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit,

b) alkanol alkoxylates of the formula (III)

R ² -O - (- AO) _m -H (m)

in which

R ^{2 is} straight-chain or branched alkyl having 4 to 20 carbon atoms,

AO for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and

Propylene oxide residues or butylene oxide residues and m stands for numbers from 2 to 20 and

c) fatty alcohol amines of the formula (IV)

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20

Carbon atoms stands and

the sum of p and q is 15 to 25,

20. The composition according to claim 1 containing

at least one solvent selected from water, methanol, ethanol, isopropanol, 1, 4-dioxane, tetrahydrofuran, dimethoxyethane, Hallcomid® (mixture of 50-60

% N, N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide),

Dimethylsulfoxide, sulfolane, N-methylpyrrolidone and gamma-butyrolactone and

at least one active compound of the formulas (I-A) or (I-B) dissolved in the above solvent,

another solvent immiscible with the above solvent which forms a separate phase and in which fenoxaprop-P-ethyl is present,

wherein the herbicidal active compounds of the formula (I-A) or (I-B) and fenoxaprop-P-ethyl are present in total in an amount of 0.2 to 50 wt .-%,

5 to 50 wt .-% of at least one surfactant selected from

a) surfactants of the formula (II):

R - Q (II)

wherein

Q -Q-SO ₃ M, -SO ₃ M, -0-PO ₃ HM or -PO ₃ HM, wherein M is hydrogen or a cation, in particular a metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion,

R is an unsubstituted or substituted C 1 -C ₃₀ -hydrocarbon radical which may optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit,

b) alkanol alkoxylates of the formula (IH)

R ² -O - (- AO) _m -H (JH)

in which

R ^{2 represents} straight-chain or branched alkyl having 4 to 20

Carbon atoms,

AO stands for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and propylene oxide radicals or butylene oxide radicals and

m stands for numbers from 2 to 20 and

c) fatty alcohol amines of the formula (IV)

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20 carbon atoms and

the sum of p and q is 15 to 25.

21. The composition according to claim 1 containing

at least one solvent selected from water, methanol, ethanol, isopropanol, 1,4-dioxane, tetrahydrofuran, dimethoxyethane, Hallcomid® (mixture of 50-60% N, N-dimethyloctanamide and 35-45% N, N-dimethyldecanamide), Dimethylsulfoxide, sulfolane, N-methylpyrrolidone and gamma-butyrolactone and

at least one active compound of the formulas (I-A) or (I-B) dissolved in the above solvent,

another solvent immiscible with the above solvent which forms a separate phase, and in which fenoxaprop-P-ethyl and mefenpyr-diethyl or

Fenoxaprop-P-ethyl and isoxadifen-ethyl are present,

the herbicidal active compounds of the formula (I-A) or (I-B) and fenoxaprop-P-ethyl and the safener (s) being present in total in an amount of 0.2 to 50% by weight,

5 to 50% by weight of at least one surfactant selected from

a) surfactants of the formula (II):

R - Q (II)

wherein

Q -0-SO ₃ M, -SO ₃ M, -0-PO ₃ HM or -PO ₃ HM,

wherein M is hydrogen or a cation, in particular a

Metal cation such as an alkali metal ion or alkaline earth metal ion, or an ammonium ion,

R is an unsubstituted or substituted C ₁ -C 30 -hydrocarbon radical which may optionally be bonded via alkylene oxide units, or R is an alkylene oxide unit,

b) alkanol alkoxylates of the formula (III)

R ² -O - (- AO) _m -H (JE)

in which

R ^{2 is} straight-chain or branched alkyl having 4 to 20 carbon atoms,

AO for an ethylene oxide radical, a propylene oxide radical, a butylene oxide radical or mixtures of ethylene oxide and Propylene oxide residues or butylene oxide residues and

m stands for numbers from 2 to 20 and

c) fatty alcohol amines of the formula (IV)

in which

R ^{3 represents} straight-chain or branched alkyl having 14 to 20 carbon atoms and

the sum of p and q is 15 to 25.

A composition according to claim 21, wherein the solvent used for the active ingredient of formula (I-A) or (I-B) is water.