EP1523236A1 - Adjuvants solides - Google Patents

Adjuvants solides

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Publication number
EP1523236A1
EP1523236A1 EP03763668A EP03763668A EP1523236A1 EP 1523236 A1 EP1523236 A1 EP 1523236A1 EP 03763668 A EP03763668 A EP 03763668A EP 03763668 A EP03763668 A EP 03763668A EP 1523236 A1 EP1523236 A1 EP 1523236A1
Authority
EP
European Patent Office
Prior art keywords
methyl
agrochemical
alkyl
plants
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03763668A
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German (de)
English (en)
Inventor
Gerhard Schnabel
Thomas Maier
Caroline Thuaud
Hans-Peter Krause
Udo Bickers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1523236A1 publication Critical patent/EP1523236A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

  • the present invention relates to new solid adjuvants, particularly those which are advantageously useful in the field of crop protection, e.g. in combination with agrochemical agents.
  • adjuvants in the form of a solid formulation are described in the literature (e.g. EP 955 810 A1, EP 955 809 A1, EP 968649 A1).
  • adjuvants have so far not been of economic relevance because they are expensive, physically not sufficiently stable in storage or not sufficiently user-friendly, e.g. insufficient disintegration in the spray liquor or large volume / weight ratio per area.
  • the object of the present invention was therefore to provide new adjuvants which have advantageous properties, in particular in combination with agrochemical active compounds, such as herbicides.
  • Adjuvants of the present invention is solved.
  • the present invention thus relates to a solid adjuvant containing
  • R 1 is H or (CC 6 ) alkyl
  • R 2 H or (dC 6 ) is alkyl
  • R 3 H is an unsubstituted or substituted C 1 -C 3 o -hydrocarbon radical, preferably (CC 30 ) Alkyl, (C 2 -C 30 ) alkenyl, (C 2 -C 30 ) alkynyl, a sulfonate residue, a phosphonate residue or an acyl residue
  • y is an integer from 1 to 1000
  • the y units (CHR 1 -CHR 2 -O) can be the same (for example ethylene oxide homopolymer units, propylene oxide homopolymer units or butylene oxide homopolymer units) or different from one another (for example ethylene oxide / propylene oxide copolymer units) or ethylene oxide / butylene oxide copolymer units).
  • Surfactants of the formula (I) are generally known, for example from "Presentation about selected Product Groups, Clariant GmbH, Surfactants Division, p.39, September 1997" and are also commercially available, for example from the Sapogenat® T series from Clariant AG.
  • catalytic conditions e.g. NaOH and / or NaAcetat; temperature approx. 100 - 200 ° C; overpressure of approx. 2 - 10 bar).
  • radicals R 1 and R 2 in formula (I ') and the radical Ar in formula (I ") are defined as in formula (I).
  • the epoxides of the formula (I 1 ) can be prepared by known methods, for example from the corresponding alkenes, and are commercially available, for example ethylene oxide or propylene oxide.
  • the compounds of the formula (I ") are commercially available and described in the literature, and they can also be prepared by standard reactions which are known to the person skilled in the art. For example, hydroxyaromatics, such as phenol, with alcohols, olefins or alkyl halides under catalytic Conditions (protonic acids such as sulfuric or phosphoric acid or Lewis acids such as aluminum chloride or boron trifluoride diethyl ether) to the compounds of formula (I ") are implemented.
  • catalytic Conditions protonic acids such as sulfuric or phosphoric acid or Lewis acids such as aluminum chloride or boron trifluoride diethyl ether
  • Preferred surfactants of the formula (I) are those in which Ar in formula (I) is a naphthyl or phenyl radical which bears 3 to 7 (-CC 10 ) alkyl radicals.
  • Ar is preferably tri (C 1 -C 6 ) alkylphenyl, particularly preferably tri-butylphenyl such as tri-2,4,6-sec-butylphenyl.
  • R 1 and R 2 are preferably H or methyl, particularly preferably H.
  • R 3 is preferably H, (-C 22 ) alkyl, (C 2 -C 22 ) alkenyl, (C 2 -C 2 2) alkynyl, an acyl radical such as CO- (CC 30 ) alkyl, CO- (C 2 -C 30 ) alkenyl, CO- (C 2 -C 30 ) alkynyl, CO- (CC 30 ) alkoxy, CO- (C 2 -C 30 ) alkenyloxy, CO- (C 2 -C 30 ) alkynyloxy or COH, or a sulfonate residue such as SO 3 M where M is a cation such as an inorganic cation, for example an alkali metal or alkaline earth metal cation such as Na, K or Mg or an organic acyl radical such as CO- (CC 30 ) alkyl, CO- (C 2 -C 30 ) alkenyl, CO- (C 2 -C 30 ) alkynyl
  • Cation e.g. a primary, secondary, tertiary or quaternary ammonium ion such as
  • Alkaline earth metal cation such as Na, K or Mg or an organic cation, for example a primary, secondary, tertiary or quaternary ammonium ion such as NH 3 CH 3 ,
  • R ' can also be Ar-0- (CHR 1 CHR 2 ) y , where Ar, R 1 , R 2 and y are as defined in formula (I).
  • R 3 H, (CC 6 ) alkyl or S0 3 M, where M is a cation, is particularly preferred.
  • Values from 15 to 100 are preferred for y, values from 30 to 80 are particularly preferred.
  • Preferred surfactants Formula (I) are solid under normal conditions (room temperature, normal pressure).
  • carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched. If not specifically stated, these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, being preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
  • Aikenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Aikenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl
  • a hydrocarbon residue means a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon residue, e.g. Alkyl, aikenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl.
  • a hydrocarbon radical preferably has 1 to 40 C atoms, preferably 1 to 30 C atoms;
  • a hydrocarbon radical is particularly preferably alkyl, aikenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl.
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.
  • the heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as a mono-, bi- or polycyclic aromatic System in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partially or fully hydrogenated radical such as oxiranyl, oxetanyl , Pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetra hydrofuryl.
  • heteroaryl such as a mono-, bi- or polycyclic aromatic System in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidiny
  • Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo.
  • the oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, aikenyl and alkynyl are partially or completely substituted alkyl, aikenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2) CH 2 CH 2 CI;
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; the same applies to haloalkenyl and other halogen-substituted radicals.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, aikenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents being, for example, one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • Substituents from the group halogen for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (CrC 4 ) haloalkyl, preferably trifluoromethyl, are generally preferred, (-C-C 4 ) alkoxy, preferably methoxy or ethoxy, (-C-C 4 ) haloalkoxy, nitro and cyano.
  • the substituents methyl, methoxy and chlorine are particularly preferred.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (CtC 4 ) alkyl, (CrC 4 ) alkoxy, (C 1 -C 4 ) haloalkyl , (-C-C 4 ) haloalkoxy and nitro is substituted, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl or 2,4,6-tributylphenyl such as 2,4,6-tri-sec-butylphenyl ,
  • An acyl residue means the residue of an organic acid which formally arises from the removal of an OH group from the organic acid, e.g. the rest of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residues of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • An acyl radical is preferably formyl or aliphatic acyl from the group CO-R x , CS-R X , CO-OR x , CS-OR x , CS-SR X , SOR ⁇ or S0 2 R ⁇ , where R x and R ⁇ each represents a C 1 -C 3 hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the latter two radicals being unsubstituted, N-monosubstituted or N, N-disubstituted.
  • Acyl means, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (CC) alkylcarbonyl, phenylcarbonyl, where the phenyl ring can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and others Remains of organic acids.
  • Formula (I) and the other formulas in this specification also include all stereoisomers and mixtures thereof. Such compounds contain a or several asymmetric carbon atoms or double bonds, which are not specified separately in the general formula.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the respective formulas and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure ones Starting materials are produced.
  • the fillers b) contained in the adjuvants according to the invention are solids. These are generally known, e.g. from: W. van Falkenburg (ed.), Pesticide Formulations, Marcel Dekker, Inc., New York, 1973; or from: Degussa No. 1 series, Synthetic Silicas for Plant Protection and Pesticides, March 1989. They are also commercially available.
  • Preferred fillers b) are e.g. inorganic or organic carriers such as polymeric carbohydrates or silicates.
  • Polymeric carbohydrates are e.g. Cellulose and its derivatives such as Tylose®, Tylopur®, Methylan® and Finnix®, or starch and its derivatives such as Maizena® and Mondamin®.
  • Silicates can be of natural or synthetic origin. Natural silicates are e.g. Kaolin, bentonite, talc, pyrophyllite or diatomaceous earth. Synthetic silicates are e.g. fumed silica or precipitated silica, e.g. Sipernat® (e.g.
  • silicates also includes silicates such as earth metal and alkaline earth metal silicates, e.g. Aluminum silicates or magnesium silicates.
  • adjuvants according to the invention are solid under normal conditions (normal pressure, room temperature).
  • Adjuvants according to the invention can be present, for example, in the form of granules, powders or dusts. They generally contain 10-80% by weight, preferably 25-75% by weight, particularly preferably 40-70% by weight, of one or more surfactants of the formula (I) and 90-20% by weight, preferably 75-25% by weight, particularly preferably 60-30% by weight, of fillers b). In In individual cases, these salary limits can also be exceeded or fallen short of.
  • Preferred adjuvants according to the invention contain the surfactants of the formula (I) in excess over the fillers b).
  • auxiliary substances is understood to mean substances which are largely chemically and biologically inert and whose use is intended to enable the intended handling of an agent.
  • auxiliary substances are:
  • Wetting agents such as Genapol ® LRO (0-20% by weight), dispersing agents such as Tamol ® (0-15% by weight) or other surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30% by weight) );
  • Inorganic salts such as NaCl, Na 2 SO, MgCl (0-50% by weight), (oligo-; poly -) - phosphates; Carbonates such as potassium carbonate;
  • Fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus and potassium-containing components, possibly further trace elements (0-60% by weight)
  • defoamers such as Fluowet ® PP (0-2% by weight);
  • Disintegrant or disintegrant such as, for example, effervescent powder (citric acid / NaHCO 3 ) (0-20% by weight), microcrystalline cellulose, polyvinylpyrrolidone;
  • Binders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinyl pyrrolidone, polyacrylic acid derivatives, (0-15% by weight); or
  • Solvents such as water or organic solvents (0-15% by weight).
  • the amounts stated for the auxiliaries are ranges which are to be regarded as typical, but which can also be exceeded or fallen short of in individual cases.
  • the adjuvants according to the invention can be prepared by known methods (cf. Hans Mollet, Arnold Grubenmann, Formuliertechnik; Wiley-VCH, Weinheim, 2000; pp. 183 ff and references given there).
  • the adjuvants can be present, for example, in the form of granules, powders or dusts.
  • Granules can be obtained, for example, by melt extrusion and subsequent granulation.
  • Powder or dusts can be obtained by pre-crushing strand pellets to the desired particle size, for example using an air jet mill.
  • the adjuvants according to the invention can be combined together with one or more agrochemical active ingredients to form agrochemicals, e.g. in the form of co-formulations or tank mixes.
  • agrochemicals are also new and the subject of the present invention.
  • Herbicides e.g. leaf-active herbicides such as ALS inhibitors (for example sulfonamides such as flucarbazone, propoxycarbazone or amicarbazone or sulfonylureas such as mesosulfuron, ethoxysulfuron, iodosulfuron, amidosulfuron, foramsulfuron), diflufenican, bromoxynil-containing phen, or loxynylapoxy-containing products, such as deroxoxylilyloxypoxides from deroxoxyliloxane-containing products, such as deroxoxyliloxane-containing products, such as deroxoxyliloxane-containing products from the class , Beet herbicides such as desmedipham, phenmedipham, ethofumesate or metamitron,
  • Herbicides contained in the agrochemical compositions according to the invention are, for example, ALS inhibitors (acetolactate synthetase inhibitors) or herbicides different from ALS inhibitors, such as herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and also Heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxazolyloxy and benzothiazolyloxyphenoxyalkane carboxylic acid esters, cyclohexanedione derivatives, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester.
  • ALS inhibitors
  • the ALS inhibitors are, in particular, imidazolinones, pyrimidinyloxy-pyridinecarboxylic acid derivatives, pyrimidyloxy-benzoic acid derivatives, triazolo-pyrimidine-sulfonamide derivatives and sulfonamides, preferably from the group of sulfonylureas, particularly preferably those with the general formula ( II) and / or their salts,
  • R ⁇ is a hydrocarbon radical, preferably an aryl radical, such as phenyl, which is unsubstituted or substituted, or a heterocyclic radical, preferably a heteroaryl radical, such as pyridyl, which is unsubstituted or substituted, and where the radicals, including substituents, contain 1-30 carbon atoms, preferably 1- Have 20 C atoms, or R a is an electron-withdrawing group such as a sulfonamide radical,
  • R ß is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and has, including substituents, 1-10 carbon atoms, for example unsubstituted or substituted CC 6 alkyl, preferably a hydrogen atom or methyl,
  • R ⁇ is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and has substituents including 1-10 C atoms, for example unsubstituted or substituted C 1 -C 6 -alkyl, preferably a hydrogen atom or methyl, x is zero or 1, and
  • R ⁇ is a heterocyclic radical.
  • ALS inhibitors are sulfonylureas of the formula (III) and / or their salts, wherein R 4 is CrC 4 alkoxy, preferably C 2 -C 4 alkoxy, or CO-R a , where R a is the same
  • R is halogen or (A) n -NR d R e , where n is zero or 1, A is a group
  • R CR'R " is in which R 'and R" are, independently of one another, the same or different H or C 1 -C 4 -alkyl, R d is H or CC 4 -alkyl and R e is an acyl radical such as formyl or CrC-alkyl Is sulfonyl, and R 5 in the event that R 4 is Cr
  • C 4 alkoxy preferably C 2 -C alkoxy, can also be H,
  • R is H or CC 4 alkyl, m is zero or 1, preferably zero,
  • X and Y are independently the same or different CrC- 6 alkyl, CrC ⁇ -alkoxy or -C-C 6 alkylthio, each of the three radicals mentioned unsubstituted or by one or more radicals from the group halogen, -CC 4 alkoxy and C- t -C- 4 alkylthio is substituted, or C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 alkenyloxy or C 3 -C 6 -Alkynyloxy, preferably CrC 4 alkyl or -CC 4 alkoxy, and
  • Z is CH or N.
  • Preferred sulfonylureas of the general formula (III) and / or their salts are those in which
  • R 4 is CO- (CrC 4 alkoxy) and R 5 is halogen, preferably iodine, or R 5 is CH 2 -NHR e , where R e is an acyl radical, preferably C 1 -C 8 -alkyl- Is sulfonyl, or b) R 4 is CO-N (C 1 -C 4 -alkyl) 2 and R 5 is NHR e , where R e is an acyl radical, preferably formyl.
  • the active ingredients from the group of ALS inhibitors such as sulfonylureas contained as a component in the herbicidal compositions according to the invention are always to be understood in addition to the neutral compounds, their salts with inorganic and / or organic counterions.
  • sulfonylureas can form salts in which the hydrogen of the -SO 2 -NH group is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines. Salt formation can also take place by addition of an acid to basic groups, such as amino and alkylamino. Suitable acids for this are strong inorganic and organic acids, for example HCl, HBr, H 2 SO or HNO 3 .
  • Preferred ALS inhibitors come from the series of sulfonylureas, for example pyrimidine- or triazinylaminocarbonyl- [benzene-, pyridine-, pyrazole-, thiophene- and (alkylsulfonyl) alkylamino -] - sulfamides.
  • Preferred substituents on the pyrimidine ring or triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or dimethylamino, where all substituents can be combined independently of one another.
  • Preferred substituents in the benzene, pyridine, pyrazole, thiophene or (alkylsulfonyl) alkylamino part are alkyl, alkoxy, halogen such as F, Cl, Br or J, amino, alkylamino, dialkylamino, acylamino such as formylamino, nitro, alkoxycarbonyl , Aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, haloalkyl, alkylcarbonyl, alkoxyalkyl, alkylsulfonylaminoalkyl, (alkanesulfonyl) alkylamino.
  • suitable sulfonylureas are A1) Phenyl- and benzylsulfonylureas and related compounds, e.g.
  • R 21 is hydrogen, halogen, cyano, (CrC 3 ) -alkyl, (-C-C 3 ) - haloalkyl, (dC ⁇ -haloalkoxy, (CC 3 ) -alkylthio, (dC 3 ) -alkoxy- (CrC 3 ) -alkyl, (-C-C 3 ) -alkoxy-carbonyl, mono- or Di - ((-CC 3 ) -alkyl) amino, (dC 3 ) -alkylsulfinyl or -sulfonyl, SO 2 -NR x R y or CO-NR x R y , in particular hydrogen,
  • R x , R y independently of one another hydrogen, (dC 3 ) alkyl, (CC 3 ) alkenyl, (dC 3 ) - alkynyl or together - (CH 2 ) 4 -, - (CH 2 ) s- or - (CH 2 ) 2-O- (CH 2 ) 2-, n is 0.1, 2 or 3, preferably 0 or 1, R 22 is hydrogen or CH 3 ,
  • R 23 is halogen, (CrC 2) alkyl, (CrC 2) alkoxy, (C ⁇ -C 2) -haloalkyl, in particular CF3, (CrC 2) -haloalkoxy, preferably OCHF2 or OCH 2 CF 3,
  • R 24 (C ⁇ -C 2) alkyl, (CrC 2) -Halogenaikoxy, preferably OCHF 2, or (C ⁇ -C 2) - alkoxy,
  • R 25 and R 26 together represent a chain of the formula - (CH 2 ) 3 SO 2 - or - (CH 2 ) 4 SO 2 -, e.g. 3- (4,6-dimethoxypyrimiden-2-yl) -1- (3rd -N-methylsulfonyl-N-methyl-aminopyridin-2-yl) sulfonylurea, or their salts;
  • R 27 ethoxy, propoxy or isopropoxy
  • R 28 halogen, N0 2 , CF 3 , CN, (-C-C 4 ) alkyl, (-C-C 4 ) alkoxy, (CC 4 ) alkylthio or (C ⁇ -C 3 ) alkoxy) carbonyl, preferably in 6-position on the phenyl ring, n 0, 1, 2 or 3, preferably 0 or 1,
  • R 29 is hydrogen, (CC 4 ) -alkyl or (C 3 -C 4 ) -alkenyl,
  • R 30 , R 31 independently of one another halogen, (dC 2 ) -alkyl, (dC 2 ) -alkoxy, (dC 2 ) - haloalkyl, (dC 2 ) -haloalkoxy or (C ⁇ -C 2 ) -alkoxy- (dC 2 ) alkyl, preferably OCH 3 or CH 3 , for example 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea, or their salts;
  • MON 37500 Sulfosulfuron (see Brighton Crop Prot. Conf. "Weeds', 1995, p. 57), and other related sulfonylurea derivatives and mixtures thereof.
  • Typical representatives of these active substances include the compounds listed below: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron, methyl-sulfonon-methyluron-methyl-sodium-methyl- Metsulfuron-Methyl, Nicosulfuron, Oxasulfuron, Primisulfuron-Methyl, Prosulfuron, Pyrazosulfuron-Ethyl, Rimsulfuron, Sulfometuron-Methyl, Sulfosulfuron, Thifensulfuron-Methyl, Triasulfuron, Tribenuron-Methyl, Triflusulfuroniums-Methyl, Iod
  • Suitable ALS inhibitors are e.g.
  • herbicidal active ingredients contained in the herbicidal compositions according to the invention which are different from ALS inhibitors are, for example: Herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives as well as heteroaryloxyphenoxyalkane carboxylic acid derivatives, such as quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxazolyloxyphenyl, phenoxyalkiono, phenoxyalkiono, phenoxyalkiono and phenoxyalkionoxybenzoxybenzoxybenzoxybenzoxy benzyl azobenzyl benzyl , Phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester.
  • Phenoxyphenoxy and heteroaryloxyphenoxy carboxylic acid esters and salts and herbicides such as bentazone, cyanazine, atrazine, dicamba or hydroxybenzonitriles such as bromoxynil and loxynil and other leaf herbicides are preferred.
  • Suitable herbicidal active substances which differ from ALS inhibitors and which may be present as a component in the agrochemical compositions according to the invention are, for example:
  • Phenoxyphenoxy and benzyloxyphenoxy carboxylic acid derivatives for example methyl 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate (diclofop-methyl), 2- (4- (4-bromo-2-chlorophenoxy) phenoxy ) methyl propionate (DE-A 26 01 548), 2- (4- (4-bromo-2-fluorophenoxy) phenoxy) methyl propionate (US-A 4,808,750), 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy ) methyl propionate (DE-A 24 33 067), 2- (4- (2-Fluoro-4-trifluoromethylphenoxy) phenoxy) propionic acid methyl ester (US-A
  • N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), N- (3-methyl-1, 2 , 4-oxadiazol-5-yl-methyl) -chloroacetic acid-2,6-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolylmethyl) -chloroacetic acid amide (metazachlor);
  • thiocarbamates e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylates);
  • K) alkyl azines e.g. as described in WO-A 97/08156, WO-A-97/31904, DE-A-19826670, WO-A-98/15536, WO-A-98/15537, WO-A-98/15538, WO- A-98/15539 and also DE-A-19828519, WO-A-98/34925, WO-A-98/42684, WO-A-99/18100, WO-A-99/19309, WO-A-99 / 37627 and WO-A-99/65882, preferably those of the formula (E)
  • L) Phosphorus-containing herbicides e.g. of the glufosinate type such as glufosinate in the narrower sense, d. H. D, L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid, glufosinate monoammonium salt, L-glufosinate, L- or (2S) -2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid , L-glufosinate monoammonium salt or bialaphos (or bilanafos), ie L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoyl-L-alanyl-L-alanine, especially its sodium salt, or of the glyphosate type such as glyphosate, i.e.
  • the herbicides of groups B to L are, for example, from the publications mentioned above and from "The Pesticide Manual”, 12th edition, 2000, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -”, by WT Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990.
  • the agrochemical compositions according to the invention contain one or more active substances from the group diflufenican, fenoxaprop-P-ethyl, metamitron, ethofumesate, phenmedipham, desmedipham or the above-mentioned group L) of the phosphorus-containing herbicides, for example glufosinate-ammonium or glyphosate.
  • the agrochemical compositions according to the invention can contain, in addition to the adjuvants according to the invention and one or more agrochemical active ingredients, further components, e.g. Formulation aids such as anti-drift agents, substances to influence moisture (humectants), fertilizers such as ammonium sulfate, urea or multi-component fertilizers e.g. based on phosphorus, potassium and nitrogen, such as P, K, N fertilizers, or commercially available surfactants other than formula (I), such as nonionic, cationic, anionic, betaine or polymeric surfactants, stabilizers such as pH stabilizers, bioeides, UV stabilizers, Defoamers, synthetic or natural polymers, solvents, e.g.
  • Formulation aids such as anti-drift agents, substances to influence moisture (humectants), fertilizers such as ammonium sulfate, urea or multi-component fertilizers e.g. based on phosphorus, potassium and nitrogen
  • polar solvents such as water or alcohols or non-polar solvents such as saturated or unsaturated aliphatic solvents which can be branched or unbranched, or aromatic solvents such as Solvesso® 100, Solvesso® 150 or Solvesso® 200 or xylene.
  • non-polar solvents such as saturated or unsaturated aliphatic solvents which can be branched or unbranched, or aromatic solvents such as Solvesso® 100, Solvesso® 150 or Solvesso® 200 or xylene.
  • the agrochemical compositions according to the invention show excellent agrochemical activity against harmful organisms such as harmful plants. Due to the improved control of the harmful plants by the agrochemical agents according to the invention, it becomes possible to reduce the application rate and / or to increase the safety margin. Both make economic and ecological sense.
  • agrochemical compositions according to the invention are characterized in that they have a synergistically effective content of a combination of the surfactants a) with fillers b) and agrochemical active ingredients c). It should especially be emphasized that even in combinations with application rates or weight ratios of a): b): c) in which one Synergism cannot always be demonstrated easily - for example because the individual compounds are usually used in combination in very different application rates or because the control of the harmful plants is already very good due to the individual compounds - the agrochemical compositions of the invention generally have a synergistic effect is inherent.
  • the agrochemical compositions according to the invention are prepared by customary processes, for example mixing by grinding, dissolving or dispersing the individual components, preferably at room temperature. An extrusion such as a melt extrusion can then take place, for example. If further auxiliaries are contained, these are also preferably entered at room temperature.
  • the order in which the individual components are added generally does not play a decisive role.
  • Components a), b) and c) of the agrochemical compositions according to the invention can be contained together in a finished formulation which can then be prepared in a conventional manner, e.g. can be applied in the form of a spray mixture or they can be formulated separately and e.g. in the tank mixing process together or separately, e.g. can be applied in succession. If the components are formulated separately, components a), b) and c) e.g. can be formulated individually or the components a) and b), a) and c) or b) and c) can be formulated together and the respective third-party component is formulated separately.
  • the adjuvants according to the invention are obtained through a suitable choice of the auxiliaries or manufacturing processes, which show a very good disintegration in the spray tank and which can also be used economically.
  • the adjuvants according to the invention can be produced in various ways, for example as granules, powders or dusts. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-dispersible granules (WG), water-soluble granules (SG) and melt granules. Granules such as melt granules are preferred.
  • WP wettable powder
  • SP water-soluble powder
  • WG water-dispersible granules
  • SG water-soluble granules
  • melt granules such as melt granules are preferred.
  • the agrochemical compositions according to the invention and the agrochemical active ingredients c) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified.
  • Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), microemulsions (ME), emulsions (EW), such as oil-in-water and water in-oil emulsions, sprayable solutions, suspension concentrates (SC), suspoemulsion concentrates (SE), oil or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powder
  • SL water-soluble concentrates
  • EC emulsifiable concentrates
  • ME microemulsions
  • Formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers", 2nd E., Darland Books, Caldwell N.J .; H. V. Olphen, "Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y. Marsden, Solvents Guide, 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual," MC Publ. Corp, Ridegewood N.J .; Sisley and Wood, “Encyclopedia of Surface Active Agents", Chem.
  • agrochemical active ingredients such as herbicides, fungicides, insecticides, as well Manufacture safeners, fertilizers and / or growth regulators, for example in the form of a ready-to-use formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to components a), b) and c), optionally diluents or inert substances and other ionic or nonionic surfactants (wetting agents, dispersing agents), e.g.
  • components a) and b) are finely ground, for example in conventional apparatus such as hammer mills, blower mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.
  • Dusts are obtained by grinding components a) and c) with finely divided solid substances such as fillers b).
  • Granules can be, for example, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules or water-dispersible granules (WG). They can be produced, for example, by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, for example polyvinyl alcohol, polyacrylic acid sodium or mineral oils, to the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture of fertilizers.
  • the agrochemical active ingredients can be ground, for example, with the surfactants of the formula (I) and the fillers b) and, if appropriate, other auxiliaries, subjected to melt extrusion and then granulated to the desired particle size.
  • Water-dispersible granules are generally prepared using the usual methods such as spray drying, fluidized bed Granulation, plate granulation, mixing with high-speed mixers and extrusion made without solid inert material. For the production of plate, fluidized bed, extruder and spray granules, see, for example, the process in "Spray-Drying Handbook" 3rd ed. 1979, G.
  • Emulsifiable concentrates are obtained by dissolving the surfactant a) and / or agrochemical active ingredient c) in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers
  • fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene.
  • Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding other surfactants, such as those e.g. already listed above for the other types of formulation.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally other surfactants, such as those e.g. already listed above for the other types of formulation.
  • EW Oil-in-water emulsions
  • the active ingredient formulations mentioned may contain the customary auxiliaries such as adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and viscosity influencing agents.
  • auxiliaries such as adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and viscosity influencing agents.
  • the formulations present in the commercial form are optionally diluted in the customary manner, e.g. for wettable powders and water-dispersible granules using water. Preparations in the form of dust, ground granules or scattering granules, are usually no longer diluted with other inert substances before use.
  • the use of the agrochemical compositions according to the invention can e.g. happen by application to the harmful organisms or the places where they occur, e.g. B. by spraying.
  • the agrochemical active ingredients c) to be used according to the invention are generally applied together with the surfactants a) and fillers b) or in succession, preferably in the form of a spray mixture which comprises the surfactants a), the fillers b) and the agrochemical active ingredients c) Contains amounts and, where appropriate, other conventional auxiliaries.
  • the spray liquor is preferably based on water and / or an oil, e.g. a vegetable oil or a high-boiling hydrocarbon such as kerosene or paraffin.
  • the agrochemical compositions according to the invention can e.g. can be implemented as a tank mix or via a co-formulation.
  • the agrochemical formulations generally contain 0.1 to 99 percent by weight, in particular 2 to 95% by weight, of agrochemical active ingredients, the following concentrations being customary, depending on the type of formulation:
  • the active ingredient concentration in wettable powders is generally about 10 to 90% by weight. -%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be about 1 to 90 % By weight, preferably 5 to 80% by weight.
  • Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
  • the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In individual cases the stated weight percentages can also be exceeded or fallen short of.
  • the spray liquor is preferably produced on the basis of water.
  • the weight ratio of surfactant (I): agrochemical active ingredient can vary within wide ranges. As a rule, it is in the range from 5000: 1 to 1: 1000, preferably 2000: 1 to 1:50, particularly preferably 1000: 1 to 1: 2.
  • the application rates of the surfactant of the formula (I) are generally between 10 and 5000 g / ha, preferably between 50 and 2000 g / ha. In individual cases, however, the specified limits can also be exceeded or fallen short of.
  • the concentration of the surfactants of the formula (I) in the spray mixture is generally between 0.001 and 4% by weight, preferably 0.01 and 2% by weight.
  • the concentration of fillers is generally between 0.001 and 4% by weight, preferably 0.01 and 2% by weight.
  • the preparation processes mentioned for the adjuvants according to the invention also allow the incorporation of agrochemical active substances, so that agrochemical agents, e.g. are available in the form of granules, powders or dusts which, in addition to the adjuvant according to the invention, also contain one or more agrochemical active ingredients.
  • the agrochemical active ingredients which can be formulated together with the surfactants of the formula (I) are preferably compounds with a Melting point greater than 80 ° C. In individual cases, the melting point of the agrochemical active ingredients can also be below 80 ° C.
  • the weight ratio between the surfactants of the formula (I) and the agrochemical active ingredients generally fluctuates between 5000: 1 - 1: 1000, and in individual cases can exceed or fall short of or exceed the stated limits. In a very particularly preferred embodiment, the weight ratio is in the range from 10: 1 to 1: 2, in particular 5: 1 to 1: 1.5.
  • the agrochemical compositions according to the invention are preferably herbicidal compositions which have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants.
  • Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients.
  • the funds can e.g. are applied in the pre-sowing, pre-emergence or post-emergence process.
  • Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.
  • Apera spica venti On the side of the monocotyledon weed species, for example, 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.
  • Apera spica venti On the side of the monocotyledon weed species, for example, 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.
  • Galium aparine such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, and convolvulus, cirsium, rumex and artemisia in the perennial weeds.
  • Harmful plants occurring in rice under the specific crop conditions e.g. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also superbly combated by the agents according to the invention.
  • herbicidal compositions according to the invention are applied to the surface of the earth before germination, either weed seedlings are prevented completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
  • the herbicidal compositions according to the invention are notable for a rapid onset and long-lasting herbicidal action.
  • the rain resistance of the active ingredients in the combinations according to the invention is generally favorable.
  • a particular advantage is the fact that the effective dosages of herbicidal compounds used in the herbicidal compositions can be set so low that their soil action is optimally low. This makes their use not only possible in sensitive crops, but groundwater contamination is practically avoided.
  • Combination of active ingredients enables a significant reduction in the amount of active ingredients required.
  • the effect in the combinations is stronger than the expected sum of the effects of the individual components used.
  • the synergistic effects allow a reduction in the application rate, the control of a broad spectrum of weeds and weeds, a faster use of the herbicidal action, a longer lasting effect, better control of the harmful plants with only one or a few applications and an expansion of the possible application period.
  • the use of the agents also reduces the amount of harmful ingredients, such as nitrogen or oleic acid, and their entry into the soil.
  • the herbicidal compositions according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds
  • crop plants of economically important crops for example dicotyledonous crops such as soybean, cotton, rape, sugar beet, or Gramineae crops such as wheat, barley, rye, oats, millet, rice, are grown or maize, only slightly or not at all damaged.
  • dicotyledonous crops such as soybean, cotton, rape, sugar beet, or Gramineae crops such as wheat, barley, rye, oats, millet, rice
  • the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
  • some of the agents according to the invention have excellent growth-regulating properties in the crop plants.
  • the agents according to the invention for controlling harmful plants can be used in genetically modified crops or crop plants obtained by mutation selection.
  • crop plants are generally distinguished by special advantageous properties, such as resistance to herbicidal compositions or resistance to plant diseases or pathogens causing plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • special properties concern e.g. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. For example, Transgenic plants with increased starch content or changed starch quality or those with a different fatty acid composition of the crop are known.
  • the agents according to the invention in economically important transgenic crops of useful and ornamental plants, for.
  • B. Gramineae crops such as wheat, barley, rye, oats, millet, rice and maize or crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the agents according to the invention can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
  • the herbicidal compositions according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic crop, for example a changed or specially expanded weed spectrum which can be controlled, changed application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
  • the present invention furthermore also relates to a process for controlling unwanted vegetation, preferably in crops such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soybeans, particularly preferably in monocotyledon crops such as cereals, e.g. Wheat, barley, rye, oats, crosses thereof such as triticale, rice, corn and millet, one or more herbicidal compositions according to the invention being applied to the harmful plants, parts of plants, plant seeds or the area on which the plants grow, e.g. applied the acreage.
  • crops such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soybeans, particularly preferably in monocotyledon crops such as cereals, e.g. Wheat, barley, rye, oats, crosses thereof such as tritica
  • the plant cultures can also be genetically modified or obtained by mutation selection and are preferably tolerant of acetolactate synthase (ALS) inhibitors.
  • ALS acetolactate synthase
  • the invention also relates to the use of the herbicidal compositions according to the invention for controlling harmful plants, preferably in plant crops.
  • the herbicidal compositions according to the invention can also be used non-selectively for combating undesirable plant growth, for example in plantation crops, on roadsides, squares, industrial plants or railway plants.
  • the agrochemical compositions according to the invention in particular herbicidal compositions, can be present both as mixed formulations, if appropriate with further agrochemical active ingredients, and auxiliaries such as additives and / or formulation auxiliaries, which are then diluted with water in the customary manner, or as so-called tank mixtures by diluting them together separately formulated or partially separately formulated components with water.
  • the combinations according to the invention achieve a reduction in the absolute application rate compared to the single application of a herbicidal active ingredient.
  • the invention therefore also relates to a process for controlling harmful plants, preferably for selectively controlling harmful plants in plant crops, characterized in that a herbicidally effective amount of the herbicides c) mentioned is used in combination with at least one of the surfactants a) and at least one filler b ) applied, e.g. in the pre-emergence, post-emergence or in the pre-and post-emergence, preferably in the pre-emergence, together or in succession, on the plants, parts of plants, plant seeds or the area on which the plants grow, e.g. the acreage.
  • the herbicides c) are applied at rates of from 0.1 to 2,000 g of active substance / ha, preferably from 0.5 to 1,000 g of active substance / ha. Also particularly preferred is the application of the active ingredients in the form of a co-formulation or in the form of tank mixtures, the individual components, e.g. in the form of formulations, mixed together in the tank with water and the spray mixture obtained is applied.
  • herbicidal compositions with the active compound combinations according to the invention are therefore used for the selective control of undesired plants.
  • the herbicidal compositions of the present invention therefore contain an additional content of one or more compounds which act as safeners or antidotes.
  • antidotes or safeners or groups of compounds which are suitable as safeners or antidots for the herbicidal compositions of the invention described above include:
  • B 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methyl-phenoxypropionic acid (mecoprop), MCPA or 3,6-dichloro-2-methoxy-benzoic acid (ester) ( dicamba).
  • h Compounds of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type, preferably 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S3-1, isoxadifen-ethyl).
  • fenclorim 46-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512
  • Daimuron 1 - (1-methyl-1-phenylethyl) -3-p-tolyl-urstoff, Pesticide Manual, 11th edition, 1997, p.
  • the components a), b) and c) of the herbicidal compositions according to the invention and the safeners mentioned can be applied together (for example as a finished formulation or in the tank-mixing method) or in succession in any order.
  • the weight ratio of safener: herbicide (compound (s) of the formula (I) and / or their salts) can vary within wide limits and is preferably in the range from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1.
  • the optimum amounts of herbicide (s) and safener (s) in each case are usually dependent on the type of herbicidal composition and / or on the safener used and on the type of crop to be treated.
  • the safeners can be used for the pretreatment of the seed of the crop (dressing of the seeds) or introduced into the seed furrows before sowing or used together with the herbicide mixture before or after emergence of the plants.
  • Pre-emergence treatment includes both the treatment of the acreage before sowing and the treatment of the sown but not yet overgrown acreage.
  • Co-application with the herbicide mixture is preferred.
  • Tank mixes or ready-to-use formulations can be used for this.
  • the application rates of the safeners can vary within wide limits and are generally in the range from 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of active compound per hectare.
  • the herbicidal compositions according to the invention can be applied in a customary manner, for example using water as a vehicle in spray liquor amounts of about 5 to 4000 liters / ha.
  • Use of the agents in the so-called low-volume and ultra-low-volume process (ULV) is just as possible as their application in the form of granules and microgranules.
  • a preferred use relates to the use of herbicidal compositions which have components a), b) and c) in a synergistically effective amount.
  • the invention also includes mixtures of one or more surfactants a), with one or more fillers b) and one or more herbicides c).
  • one, two or more agrochemical active ingredients e.g. insecticides, fungicides, safeners
  • insecticides, fungicides, safeners which are different from the herbicides c
  • various herbicidal active compounds of the formula (III) and / or their salts can be combined with one another, for example mesosulfuron-methyl + iodosulfuron-methyl, mesosulfuron-methyl + iodosulfuron-methyl-sodium, mesosulfuron-methyl + foramsulfuron, mesosulfuron -methyl + foramsulfuron, mesosulfuron-methyl-sodium + iodosulfuron-methyl, mesosulfuron-methyl-sodium + iodosulfuron-methyl-sodium, mesosulfuron-methyl-sodium + foramsulfuron, mesosulfuron-methyl-sodium + foramsulfuron, mesosulfuron-methyl-sodium + foramsulfuron, Foramsulfuron + iodosulfuron-methyl, foramsul
  • herbicidal active ingredients c) and their mixtures e.g. the aforementioned active ingredient mixtures of active ingredients of the formula (III) and / or their salts can be combined with one or more safeners, in particular with the safeners mefenpyr-diethyl (S1-1), cloquintocet-mexyl (S2-1) and isoxadifen-ethyl (S3-1).
  • safeners mefenpyr-diethyl (S1-1), cloquintocet-mexyl (S2-1) and isoxadifen-ethyl (S3-1).
  • the adjuvants according to the invention have high physical stability and a high surfactant load and are also ecologically advantageous. They are also suitable for the production of agrochemicals that have a high biological effectiveness, a high active ingredient load and an excellent tank mix quality.
  • a mixture of 50 g Sapogenat ® T500, 20 g Sipernat ® 50S, 10 g Atlox ® Metasperse 150S, 5 g Morwet ® EFW, 10 g ammonium sulfate, 5 g effervescent powder (citric acid / sodium hydrogen carbonate) is mixed in a kneader (LUK 025TV from Werner and Pfleiderer) mixed thoroughly at temperatures of 80-100 ° C (duration: 40 min.).
  • the mixture is then transferred to a benchtop pelletizer (Benchtop KAR-75) and to extrusion granules transferred.
  • the dispersibility as well as the suspendability of the samples thus obtained indicated very good quality according to CIPAC measurement methods, even after the samples had been stored after 2 weeks at 54 ° C.
  • 31 g lumpy Sapogenat ® T500 were ground on an IKA laboratory mill to a grain size of approx. 200 ⁇ , and in a kitchen mixer with 21.05 g glufosinate ammonium, 16.75 g Sipernat ® 350 (highly disperse silica), 3.04 g Atlox ® Metasperse 150S, 5.10g Genapol ® LRO (paste, 69%), 0.06g Fluowet ® PP, 20g ammonium sulfate and 3g Agrimer ® XLF intimately mixed.
  • This premix was metered by means of a vibrating trough into a melt extrusion apparatus from Thermo-Prism (type twin-screw extruder Eurolab 16mm) and through a multi-hole nozzle with 0.7mm holes extruded.
  • the operating temperature was 25 ° C in the feed area, 65 ° C in the entire mixing and kneading zone, and 60 ° C directly in front of the nozzle.
  • the extrudate solidified within a few seconds after leaving the extruder and was broken into pieces approximately 3 mm long.
  • the dispersibility of the extrudate was measured under conditions according to CIPAC MT174 and was 70% by weight. This method is described in: CIPAC Handbook, Collaborative International Pesticides Analytical Council Ltd 1995: Physico-chemical Methods for Technical and Formulated Pesticides, Vol. F, page 435.
  • Example 6 was repeated with the only difference that glyphosate was used as the active ingredient instead of glufosinate ammonium.
  • the dispersibility of the extrudate was 76% by weight.
  • Genapol ® LRO (paste, 69%) lauryl ethoxyl ether sulfate (Clariant)
  • Genapol ® X-150 isotridecyl alcohol ethoxylate (Clariant) Kaolin ® 1777 clay (Ziegler, Wunsiedel) Atlox Metasperse ® 150S styrene-acrylic acid copolymer (Uniquema) Steamic ® OOS aluminum hydrosilicate (Tale de Luzenac) Morwet ® EFW alkylnaphthalenesulfonic acid derivative (Akzo Nobel) Fluowet ® PP perfluoroalkylphosphonic acid (Clariant)

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Adjuvant solide qui contient (a) un ou plusieurs tensioactifs de formule Ar-O-(CHR<1>-CHR<2>-O-)y-R<3> dans laquelle Ar représente aryle substitué par un ou plusieurs radicaux alkyle (C1-C30), R<1> représente H ou alkyle (C1-C6), R<2> représente H ou alkyle (C1-C6), R<3> représente H, un radical hydrocarbure (C1-C30) non substitué ou substitué, un radical sulfonate, un radical phosphonate ou un radical acryle et y représente un nombre entier de 1 à 100, et (b) une ou plusieurs matières de charge. Ledit adjuvant est particulièrement adapté pour la protection phytosanitaire.
EP03763668A 2002-07-12 2003-06-30 Adjuvants solides Withdrawn EP1523236A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10231615 2002-07-12
DE10231615A DE10231615A1 (de) 2002-07-12 2002-07-12 Feste Adjuvantien
PCT/EP2003/006933 WO2004006671A1 (fr) 2002-07-12 2003-06-30 Adjuvants solides

Publications (1)

Publication Number Publication Date
EP1523236A1 true EP1523236A1 (fr) 2005-04-20

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EP03763668A Withdrawn EP1523236A1 (fr) 2002-07-12 2003-06-30 Adjuvants solides

Country Status (16)

Country Link
US (1) US20040013678A1 (fr)
EP (1) EP1523236A1 (fr)
JP (1) JP2005533091A (fr)
KR (1) KR20050021460A (fr)
CN (1) CN1668190A (fr)
AR (1) AR040479A1 (fr)
AU (1) AU2003258502A1 (fr)
BR (1) BR0312628A (fr)
CA (1) CA2492679A1 (fr)
DE (1) DE10231615A1 (fr)
HR (1) HRP20050023A2 (fr)
MX (1) MXPA05000507A (fr)
RU (1) RU2005103817A (fr)
TW (1) TW200402263A (fr)
WO (1) WO2004006671A1 (fr)
ZA (1) ZA200410131B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10201391A1 (de) * 2002-01-16 2003-07-31 Bayer Cropscience Ag Verwendung von Alkoholethoxylaten als Penetrationsförderer
AU2006200731B2 (en) * 2005-03-31 2011-05-19 Sumitomo Chemical Company, Limited Emulsifiable concentrate
EP1836894A1 (fr) * 2006-03-25 2007-09-26 Bayer CropScience GmbH Nouvelles formulations solides à base de sulfonamides
EA200800751A1 (ru) * 2005-09-08 2008-08-29 Байер Кропсайенс Аг Новые сульфонамидсодержащие твердые препараты
KR20140097573A (ko) * 2011-12-15 2014-08-06 바스프 에스이 살충제 및 폴리알콕실레이트의 용융물로부터 제조되며, 임의로는 폴리카르복실레이트로 착물형성된 액체 아쥬반트를 함유하는 고체 농약제형물
US20160244390A1 (en) * 2013-10-07 2016-08-25 Clariant International Ltd. Etherified Tri-Butylphenol Alkoxylates, Process For Their Preparation And Their Use In Crop Protection Agents
EP3210468A1 (fr) * 2016-02-26 2017-08-30 Bayer CropScience Aktiengesellschaft Compositions sans solvant pour agents actifs a bas point de fusion

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Publication number Priority date Publication date Assignee Title
GB1561974A (en) * 1975-07-04 1980-03-05 Reckitt & Colmann Prod Ltd Coating compositions
HU196885B (en) * 1985-10-01 1989-02-28 Mta Koezponti Kemiai Kutato In Herbicides containing as active substance aryloxiphenoxi-acyl-malonic acid esthers and process for production of the active substances
EP0541056B1 (fr) * 1991-11-08 1996-06-12 Hoechst Schering AgrEvo GmbH Granulés dispersibles dans l'eau de suspoémulsions
DE4239181A1 (de) * 1992-11-03 1994-05-05 Hoechst Ag Wirkungsverstärkung von Neophanen, Azaneophanen und anderen Wirkstoffen durch Penetrationsmittel
EP0971590B1 (fr) * 1997-03-24 2003-05-28 Basf Aktiengesellschaft Melanges solides a base de sulfonylurees et adjuvants
EP0968649A1 (fr) * 1998-07-02 2000-01-05 E.I. Du Pont De Nemours And Company Adjuvants pour compositions herbicides solides
DE10022989A1 (de) * 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Kombinationen von Pflanzenschutzmitteln mit organischen oder anorganischen Trägermaterialien
KR20030017549A (ko) * 2000-06-19 2003-03-03 바이엘 크롭사이언스 게엠베하 제초제
DE10063960A1 (de) * 2000-12-20 2002-06-27 Aventis Cropscience Gmbh Herbizide Mittel

Non-Patent Citations (1)

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Title
See references of WO2004006671A1 *

Also Published As

Publication number Publication date
WO2004006671A1 (fr) 2004-01-22
US20040013678A1 (en) 2004-01-22
ZA200410131B (en) 2006-07-26
BR0312628A (pt) 2005-04-19
AR040479A1 (es) 2005-04-06
AU2003258502A1 (en) 2004-02-02
CN1668190A (zh) 2005-09-14
RU2005103817A (ru) 2005-08-10
CA2492679A1 (fr) 2004-01-22
TW200402263A (en) 2004-02-16
MXPA05000507A (es) 2005-03-23
JP2005533091A (ja) 2005-11-04
DE10231615A1 (de) 2004-02-05
KR20050021460A (ko) 2005-03-07
HRP20050023A2 (en) 2006-02-28

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