[go: up one dir, main page]

EP2117317A2 - Penetration enhancer for herbicides and safeners - Google Patents

Penetration enhancer for herbicides and safeners

Info

Publication number
EP2117317A2
EP2117317A2 EP07856448A EP07856448A EP2117317A2 EP 2117317 A2 EP2117317 A2 EP 2117317A2 EP 07856448 A EP07856448 A EP 07856448A EP 07856448 A EP07856448 A EP 07856448A EP 2117317 A2 EP2117317 A2 EP 2117317A2
Authority
EP
European Patent Office
Prior art keywords
methyl
alkyl
cyprosulfamide
ethyl
group
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.)
Withdrawn
Application number
EP07856448A
Other languages
German (de)
French (fr)
Inventor
Peter Baur
Ronald Vermeer
Rainer Süssmann
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
Original Assignee
Bayer CropScience AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Priority to EP07856448A priority Critical patent/EP2117317A2/en
Publication of EP2117317A2 publication Critical patent/EP2117317A2/en
Withdrawn legal-status Critical Current

Links

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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the invention relates to the field of chemical crop protection, in particular the use of a special compound as a penetration promoter for agrochemical active substances from the group of herbicides and safeners and
  • Plant protection product containing this compound.
  • the compound is tributoxyethyl phosphate (CAS Regno: 78-51-3, hereinafter referred to as TBEP).
  • penetration promoter is understood to mean compounds which promote the uptake of herbicides and safeners, alone or in a mixture, through the cuticle of a plant into the plant, ie accelerate the absorption rate and / or increase the absorbed amount of the active substance into the plant.
  • Substances which increase the penetration of herbicides and / or safeners through the cuticle of the plant are valuable auxiliaries in chemical crop protection.
  • Various classes of substances are already known as penetration enhancers (see for example WO 2005/104844 A).
  • DE 3513889 A1 generally treats penetration promoters as "activators" for biocides and
  • EP 579052 A2 describes compounds from the group of alkyl phosphates, such as tributyl phosphate and tripropyl phosphate, as penetration promoters. Nevertheless, there is still a need for further compounds with more advantageous properties from a variety of viewpoints.
  • the object of the invention is therefore to provide further advantageous substances with penetration-promoting properties for agrochemical active ingredients. It has now surprisingly been found that the solvent TBEP, in contrast to many other solvents in certain lower application rates and certain mixing ratios to the active ingredient to increase the penetration of herbicides and safeners, alone or in mixture, by the cuticle of the plant and thus to increase biological activity of plant protection products.
  • TBEP is already known as a solvent in correspondingly high application rates in crop protection, as in herbicides (see, for example, WO 01/47356 A1, EP 1251736 B1, WO 00/56146 A1, EP 1164842 B1) and insecticides (see, for example, JP 08291004 A, US 5674517 A). From GB 2022070 A TBEP is known for defoliation, wherein it was added in ratios of (TBEP: active ingredient) 2: 1 to 4: 1 to the herbicidal active ingredients. In the field of fungicides, the use of TBEP as a penetration promoter still seems to be unknown.
  • the invention relates to a method for promoting penetration, wherein the components
  • A one or more active substances from the group of herbicides and / or safeners
  • B tributoxyethyl phosphate
  • C optionally one or more emulsifiers, preferably from
  • the invention likewise relates to the use of the method described here, wherein the components are applied simultaneously or sequentially to the harmful plants.
  • herbicides include plant growth regulators, and from the group of safeners, as well as plant nutrients which have systemic properties, and as a combination partner candidate contact agents.
  • herbicides includes both herbicides and plant growth regulators unless the context otherwise indicates.
  • systemic agents i. those that are absorbed by the plant through the leaves or over the roots and passed on in the juice stream, the transport system or plant.
  • active compounds which have a Log P value of ⁇ 4 (determined according to EEC Directive 79/831 Annex V. A8 by HPLC, gradient method, acetonitrile / 0.1% aqueous phosphoric acid), in particular those having a Log P value of ⁇ 4 and> 0.1.
  • Examples of individual active substances from the group of herbicides, including plant growth regulators, and from the group of safeners are:
  • herbicides are, for example, ALS inhibitors (acetolactate synthetase inhibitors) or herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and heteroaryloxy-phenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyl oxy-, pyridyloxy-, benzoxazolyloxy- and benzthiazolyloxyphenoxyalkane-carboxylic acid esters, cyclohexanedione derivatives, imidazolinones, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, pyrimidinyloxy pyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidine-sulfonamide derivatives and S- (
  • sulphonylureas are always to be understood as meaning, in addition to the neutral compounds, their salts with inorganic and / or organic counterions.
  • sulfonylureas can form, for example, 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 else ammonium salts or salts with organic amines.
  • salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Preferred ALS inhibitors are derived from the series of sulfonylureas and / or their salts, e.g. Pyrimidine or triazinylaminocarbonyl [benzene, pyridine, pyrazole, thiophene and (alkylsulfonyl) alkylamino] sulfamides.
  • sulfonylureas e.g. Pyrimidine or triazinylaminocarbonyl [benzene, pyridine, pyrazole, thiophene and (alkylsulfonyl) alkylamino] sulfamides.
  • suitable sulfonylureas are, for example
  • E is CH or N, preferably CH, R 20 is iodine or NR 25 R 26 ,
  • R 21 is hydrogen, halogen, cyano, (C r C 3 ) -alkyl, (C 1 -Ca) -alkoxy, (C 1 -C 3 ) -haloalkyl, (C 1 -C 3 ) -haloalkoxy, (C r C 3 ) -Alkylthio, (CrC 3 ) -alkoxy- (d-)
  • R x, R y are independently hydrogen, (C r C 3) alkyl, (Ci-C 3) -alkenyl, (C 1 -C 3) - alkynyl or together are - (CH 2) 4 -, - (CH 2 ) Is 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, (C r C 2) alkyl, (dC 2) alkoxy, (CrC 2) -haloalkyl, in particular CF3, (CrC 2) -haloalkoxy, preferably OCHF2 or OCH 2 CF 3 ,
  • R 24 (-C 2) alkyl, (CrC 2) -haloalkoxy, preferably OCHF2, or (C 1 -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 -, for example 3- (4,6-dimethoxypyrimiden-2-yl) -1- (3 -N-methylsulfonyl-N-methyl-aminopyridin-2-yl) -sulfonylurea, or salts thereof;
  • Alkoxyphenoxysulfonylureas as described e.g. in EP-A 0 342 569, preferably those of the formula
  • E is CH or N, preferably CH
  • R 27 is ethoxy, propoxy or isopropoxy
  • R 28 is halogen, NO 2, CF 3, CN, (C r C4) alkyl, (C r C4) alkoxy, (C r C4) alkylthio or
  • (C 1 -C 3 ) -alkoxycarbonyl preferably in the 6-position on the phenyl ring, n is 0, 1, 2 or 3, preferably 0 or 1, R 29 is hydrogen, (C 1 -C 4 ) -alkyl or (C 3 -) C 4 ) alkenyl,
  • R 30, R 31 are independently halogen, (CrC 2) alkyl, (CrC 2) alkoxy, (C 1 -C 2) - haloalkyl, (dC 2) -haloalkoxy or (CrC 2) alkoxy (CrC 2 ) alkyl, preferably OCH 3 or CH 3 , for example 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea, or salts thereof;
  • imidazolylsulfonylureas eg MON 37500, sulfosulfuron (see Brighton Crop Prot. Conf., Weeds 1 , 1995, p. 57), and other related sulfonylurea derivatives and mixtures thereof;
  • Typical representatives of these active ingredients include the following compounds: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl-sodium, halosulfuron-methyl, imazosulfuron, Metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, iodosulfuron-methyl and its sodium salt (WO
  • N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), NKS-methyl-1-oxadiazol-6-yl-methoxy-chloroacetic acid, 1-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 (butylate);
  • cyclohexanedione oximes e.g. 3- (1-Allyloxyiminobutyl) -4-hydroxy-6,6-dimethyl-2-oxo-cyclohex-3-encarboxylic acid methyl ester, (alloxydim),
  • imidazolinones e.g. Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2 yl) -4-methylbenzoic
  • Triazolopyrimidinesulfonamide derivatives eg N- (2,6-difluorophenyl) -7-methyl-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (flumetsulam), N- (2,6 Dichloro-3-methylphenyl) -5,7-dimethoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide,
  • S- (N-aryl-N-alkyl-carbamoylmethyl) -dithiophosphonic acid esters such as S- [N- (4-chloro-phenyl) -N-isopropyl-carbamoyl-methyl] -O, O-dimethyl-dithiophosphate (anilophos).
  • Alkylazines for example 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 (K)
  • H is R 1 (C r C 4 ) alkyl or (C r C 4 ) haloalkyl;
  • R 2 is (C 1 -C 4 ) alkyl, (C 3 -C 6 ) -cycloalkyl or (C 3 -C 6 ) -cycloalkyl (C 1 -C 4 ) -alkyl and
  • A is -CH 2 -, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, -O-, -CH 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -O- mean, particularly preferably those of the formula K1-K7
  • L) phosphorus-containing herbicides e.g. one or more compounds of the formula (IV) or derivatives thereof, such as salts,
  • active compounds of the formula (IV) and (V) are the following:
  • auxins and auxin analogs e.g. 4-indole-3-butyric acid, indole-3-acetic acid, 1-naphthylacetic acid, 2- (1-naphthyl) acetamide and 2-naphthyloxyacetic acid;
  • cytokinins e.g. Cythokinin, Kinetin and 6-Benzylaminopurine;
  • gibberellins e.g. Gibberillic Acid, Gibberillin A4 and A7;
  • T) ethylene precursors e.g. ethephon
  • U) herbicides from the group of fatty acid synthetase inhibitors eg chlorotoluron, dimefuron, diuron, fluometuron, isoproturon, isourone, carbutilates, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron and tebuthiuron and
  • hydroxybenzonitriles e.g. such as bromoxynil and loxynil and their salts and esters such as bromoxyniloctanoate and loxyniloctanoate.
  • the agrochemical active substances can also be growth regulators. Examples of these are ethephon, tribufos, cyclanilides and thidiazuron.
  • herbicides plant growth regulators
  • groups A to X for example, from the above-mentioned writings and / or from "The Pesticide Manual", 12th edition (2000) to 14th edition (2006), 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.
  • safeners examples include:
  • n ' is a natural number from 0 to 5, preferably 0 to 3
  • T is a (Ci or C2) -alkanediyl chain which is [alkoxy (C 3 r C)] is carbonyl unsubstituted or substituted with one or two (CrC 4) alkyl or;
  • W is an unsubstituted or substituted divalent heterocyclic radical from the group of unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring N or O atoms, at least one N atom and at most one O atom in the ring, preferably a radical from the group (W1) to (W4),
  • R 17 , R 19 are identical or different halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, nitro or (C r C 4 ) haloalkyl;
  • R 18 , R 20 are identical or different OR 24 , SR 24 or NR 24 R 25 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S. which is connected via the N atom to the carbonyl group in (S-II) or (S-III) and unsubstituted or by radicals from the group (C 1 -C 4 ) alkyl,
  • R 24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;
  • R 25 is hydrogen, (CrC 6) alkyl, (C r C6) alkoxy, or substituted or unsubstituted phenyl;
  • R x is H, (C r C ⁇ ) alkyl, C r C 8 (haloalkyl), (Ci-C 4 ) alkoxy (C 1 -C 8 ) alkyl, cyano or COOR 26 , wherein R 26 is hydrogen, (C r C 8 ) alkyl, (C r C 8 ) haloalkyl, (C r C 4 ) alkoxy (Ci-C 4) alkyl, (CrCeJHydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (Ci-C4) alkyl silyl;
  • R 27 , R 28 , R 29 are identical or different hydrogen, (C 1 -C 8 ) alkyl,
  • R 21 is (CrC 4) alkyl, (C r C4) haloalkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl, (C 3 -C 7) cycloalkyl, preferably dichloromethyl;
  • R 22 , R 23 is identical or different hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl,
  • N1, N2-diallyl-N2-dichloroacetylglycine amide (DKA-24 (IV-3), from HU 2143821), 4-dichloroacetyl-1-oxa-4-aza-spiro [4,5] decane (AD-67), 2,2-dichloro-N- (1,3-dioxolan-2-ylmethyl) -N- (2-propenyl) acetamide (PPG-1292), 3-dichloroacetyl-2,2,5- trimethyloxazolidine (R-29148, IV-4), 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine, 3-dichloroacetyl-2,2-dimethyl-5- (2-thienyl) oxazolidine,
  • R 30 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro , Amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula -Z a -R a is substituted, wherein each hydrocarbon moiety preferably 1 to 20 carbon atoms and a C-containing radical R 30 including substituents preferably 1 to 30 Having C atoms;
  • R 31 is hydrogen or (dCO-alkyl, preferably hydrogen, or R 30 and R 31 together with the group of the formula -CO-N- the radical of a 3- to 8-membered saturated or unsaturated ring;
  • R 32 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH 2 , SO 2 NH 2 or a radical of the formula -Z b -R b ;
  • R 33 is hydrogen or (dCO-alkyl, preferably H;
  • R 34 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH 2 , SO 2 NH 2 or a radical of the formula -Z c -R c ;
  • R a is a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [(Ci-C 4 ) - alkyl] -amino, or an alkyl radical in which several, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom;
  • R b , R c identically or differently, are a hydrocarbon radical or a
  • Heterocyclyl radical wherein each of the last two radicals unsubstituted or by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halogeno (C 1 -C 0 -alkoxy, mono- and di- [(C 1 -C 4 ) -alkyl] -amino is substituted, or an alkyl radical in which a plurality, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom;
  • Z a is a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-,
  • Z b , Z c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO 2 -, -NR * -, -SO 2 -NR * -, -NR * -SO 2 -, -CO-NR * - or -NR * -CO-, where the bond of the respective divalent group indicated on the right is the bond to the radical R b or R c and where the R * in the last-mentioned 5 radicals are each independently H, (Ci-C4) -alkyl or halo- (CrC 4 ) - alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular O or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2;
  • R 30 cyclopropyl
  • R 34 2-OMe is (V-3)
  • R 30 cyclopropyl
  • R 34 2-OMe-5-CI is (V-4)
  • R 30 cyclopropyl
  • R 34 2-Me is (V-5)
  • X 3 is CH or N
  • R 35 is hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 and Z a -R are a substituted;
  • R 36 is hydrogen, hydroxy, (CrC 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkynyl, (C 1 -C 6) -
  • R 35 and R 36 together with the nitrogen atom carrying them have a 3- to 8-membered saturated or unsaturated ring;
  • R 37 is halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 or Z b -R b ;
  • R 38 is hydrogen, (C 1 -C 4 ) -alkyl, (C 2 -C 4 ) -alkenyl or (C 2 -C 4 ) -alkynyl;
  • R 39 is halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH 2 ,
  • R a is a (C 2 -C 2 o) -alkyl radical whose carbon chain is mono- or interrupted by oxygen atoms, is heterocyclyl or a hydrocarbon radical, where the last two radicals are optionally substituted by one or more identical or different radicals from the group halogen substituted [(C r C 4) -alkyl] amino - cyano, nitro, amino, hydroxyl, mono- and di;
  • R b , R c identically or differently, denote a (C 2 -C 20 ) -alkyl radical whose carbon chain is interrupted one or more times by oxygen atoms, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C 1 -C 4 ) -
  • Z a is a divalent unit from the group O, S 1 CO 1 CS 1 C (O) O, C (O) S, SO, SO 2 ,
  • NR d C (O) NR d or SO 2 NR d ;
  • Z b , Z c identically or differently, denote a direct bond or a divalent unit from the group O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , SO 2 NR d or
  • R d is hydrogen, (C r C 4 ) -alkyl or (Ci-C 4 ) -haloalkyl; n is an integer from 0 to 4, and m in the case that X is CH, an integer from 0 to 5, and for the
  • X is N, an integer from 0 to 4; preferably safeners of compounds of the formula (S-VI) in which X 3 CH;
  • R 35 is hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 2 -C 6 ) -alkenyl, (C 5 -C 6 ) -cycloalkenyl, phenyl or 3 to 6-membered heterocyclyl with up to three
  • R 36 is hydrogen, (C 1 -C 6 -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, where the last three radicals mentioned are optionally substituted by one or more, identical or different substituents from the group consisting of halogen , Hydroxy, (C 1 -C 4 ) -
  • R 37 is halogen, (Ci-C 4) -haloalkyl, (Ci-C 4) -haloalkoxy, nitro, (CrC 4) alkyl, (C 1 -C 4) -
  • R 38 is hydrogen
  • R 39 is halogen, nitro, (C r C4) alkyl, (C 1 -C 4) -haloalkyl, (Ci-C 4) -haloalkoxy, (C 3 -C 6) -
  • alkylcarbonyl n is 0, 1 or 2 and m is 1 or 2.
  • R ⁇ and R ß independently hydrogen, d-Ce-alkyl, alkyl-C 3 -Cs CyClOaI, C 3 -C 6 alkenyl, C 3 -C 6 kinyl Al,
  • substituted C 1 -C 4 -alkoxy, or R ⁇ and R ß together are a C 4 -C 6 alkylene or by oxygen, sulfur, SO, SO 2, NH or -N (C r C 4 alkyl) - interrupted C 4 -C 6 - alkylene bridge,
  • R ⁇ is hydrogen or C 1 -C 4 -alkyl
  • R a and R b independently represent hydrogen, halogen, cyano, nitro, trifluoromethyl, -C 4 alkyl, C 1 -C 4 -alkoxy, C r C 4 alkylthio, C r C 4 alkylsulfinyl,
  • R 9 and R h independently of one another represent hydrogen, halogen, C 1 -C 4 -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ', where
  • R c is hydrogen, halogen, C 1 -C 4 -alkyl or methoxy
  • R d is hydrogen, halogen, nitro, Ci-C 4 alkyl, -C 4 alkoxy, -C 4 alkylthio, C 1 -C 4 -
  • R d and R e together represent a C 3 -C 4 -alkylene bridge
  • R f is hydrogen, halogen or C 1 -C 4 -alkyl
  • R x and R ⁇ independently represent hydrogen, halogen, C 4 alkyl, Ci-C 4 -
  • R J, R k and R m are independently hydrogen or C- ⁇ -C 4 alkyl, R k and R m together form a C 4 - C 6 alkylene bridge or an interrupted by oxygen, NH or -N (C 1 -C 4 alkyl) - Cj-C ⁇ -alkylene bridge, and
  • R n is C 1 -C 4 -alkyl, phenyl or by halogen, C 1 -C 4 -alkyl, methoxy, nitro or
  • Trifluoromethyl substituted phenyl preferably safeners of the formula (S-VIII)
  • radicals in the formulas (S-II) to (S-VIII) can each be straight-chain or branched in the carbon skeleton.
  • Alkyl radicals even in the composite meanings such as alkoxy, haloalkyl, etc., preferably have 1 to 4 carbon atoms and, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl.
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl is, 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-but-2-en-1-yl.
  • Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl.
  • (C 1 -C 4 ) -alkyl is the Short for alkyl having 1 to 4 carbon atoms; the same applies to other general remainder definitions with bracketed ranges for the possible number of C atoms.
  • Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, particularly preferably 3 to 6, C atoms, for example cyclopropyl,
  • Cyclobutyl, cyclopentyl and cyclohexyl refer to corresponding unsaturated compounds.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl, haloalkenyl and haloalkynyl by halogen preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or fully substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF 2 CF 3 , CH 2 CHFCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl.
  • Haloalkoxy is eg OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl.
  • a hydrocarbon radical can be an aromatic or an aliphatic hydrocarbon radical, where an aliphatic hydrocarbon radical is generally a straight-chain or branched saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, particularly preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl.
  • an aliphatic hydrocarbon radical alkyl, alkenyl or alkynyl having up to 12 carbon atoms; the same applies to an aliphatic hydrocarbon radical in a Kohlenwasserstoffoxyrest.
  • Aryl is generally a mono-, bi- or polycyclic aromatic system having preferably 6-20 C atoms, preferably 6 to 14 C atoms, more preferably 6 to 10 C atoms, e.g. Phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl and fluorenyl, more preferably phenyl.
  • Heterocyclic ring, heterocyclic radical or heterocyclyl means a mono-, bi- or polycyclic ring system which is saturated, unsaturated and / or aromatic and contains one or more, preferably 1 to 4, heteroatoms, preferably from the group N, S and O.
  • Preferred are saturated heterocycles having 3 to 7 ring atoms and one or two heteroatoms from the group N, O and S, wherein the chalcogens are not adjacent.
  • Particularly preferred are monocyclic rings having 3 to 7 ring atoms and a heteroatom from the group N, O and S, as well as morpholine, dioxolane, piperazine, imidazoline and oxazolidine.
  • Very particularly preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran. Also preferred are partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms from the group N, O and S. Particularly preferred are partially unsaturated heterocycles having 5 to 6 ring atoms and one heteroatom from the group N, O and S. Very particular preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline. Also preferred is heteroaryl, for example mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms containing one to four heteroatoms from the group N, O, S, wherein the chalcogens are not adjacent.
  • monocyclic aromatic heterocycles having 5 to 6 ring atoms which contain a heteroatom from the group, N, O and S, and pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and isoxazole.
  • pyrazole, thiazole, triazole and furan are particularly preferred.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, such as phenyl and arylalkyl, such as benzyl, or substituted heterocyclyl, represent a substituted radical derived from the unsubstituted radical, where the substituents are preferably one or more, preferably 1, 2 or 3 , in the case of Cl and F also up to the maximum possible number, substituents 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, alkylsulfon
  • substituents from the group halogen for example fluorine or chlorine, (C 1 -C 4 ) -alkyl, preferably methyl or ethyl, (C 1 -C 4 -haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) -alkoxy, preferably methoxy or ethoxy, C 4 ) haloalkoxy, nitro and Cyano.
  • substituents from the group halogen for example fluorine or chlorine
  • C 1 -C 4 -haloalkyl preferably trifluoromethyl
  • C 1 -C 4 ) -alkoxy preferably methoxy or ethoxy, C 4 ) haloalkoxy
  • Particularly preferred are the substituents methyl, methoxy and chlorine.
  • Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are N-substituted by, for example, one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles.
  • alkyl radicals having 1 to 4 carbon atoms are preferred.
  • Aryl is preferably phenyl.
  • Substituted aryl is preferably substituted phenyl. This is true for acyl the definition mentioned further below applies, preferably (CrC 4) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, in halogens such as Cl and F also up to five times, by identical or different radicals from the group halogen, (C r C 4 ) alkyl, ( C r C 4 ) alkoxy, (C 1 -C 4 ) haloalkyl, (C r C 4 ) haloalkoxy and nitro, 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.
  • halogens such as Cl and F also up to five times
  • An acyl radical is the radical of an organic acid having preferably up to 6 C atoms, for example the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the radical of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids , Sulfinic acids, phosphonic acids, phosphinic acids.
  • Acyl for example, formyl, alkylcarbonyl, such as (C r C 4 alkyl) carbonyl, phenylcarbonyl, wherein the phenyl ring may be substituted, for example as above
  • stereoisomers which have the same topological linkage of the atoms, and mixtures thereof.
  • Such compounds contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formulas.
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
  • the compounds of formula (S-II) are e.g. from EP-A-0333131 (ZA-89/1960), EP-A-0269806 (US 4,891,057), EP-A-0346620 (AU-A-89/34951), EP-A-0174562, EP-A No.
  • the compounds of formula (S-IV) are known from numerous patent applications, for example US 4,021,224 and US 4,021,229.
  • Compounds of subgroup b) are further from CN-A-87/102789, EP-A-365484 and from "The Pesticide Manual", 11th to 13th edition, British Crop Protection Council and the Royal Society of Chemistry (1997), known.
  • the compounds of subgroup c) are described in WO-A-97/45016, those of subgroup d) in WO-A-99/16744 (in particular in EP-A-365484).
  • the cited documents contain detailed information on preparation processes and starting materials and name preferred compounds. These documents are expressly referred to, they are by quotation as part of this description.
  • the safeners of the above groups a) to e) reduce or prevent the phytotoxic effects which can occur when using the herbicidal compositions according to the invention in crops without impairing the effectiveness of the herbicides against harmful plants.
  • the field of application of the herbicides can be significantly extended and in particular by the use of safeners, the use of herbicides, which have so far only limited or could be used with insufficient success, ie of combinations without Safener in low dosages with little broader effect led to insufficient control of harmful plants.
  • safeners in the formulations according to the invention, inter alia: 4-dichloroacetyl-1-oxa-4-aza-spiro [4.5] -decane (AD-67), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo [1,2-a] pyrimidine-6 (2H) -one (dicyclonone, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (Benoxacor), cloquintocet , 5-chloro-quinolin-8-oxy-acetic acid (1-methyl-hexyl ester) (cloquintocet-mexyl), ⁇ - (cyanomethoxyimino) -phenylacetonitrile (cyometrinil), 2,2-dichloro-N- (2-oxo) 2- (2-propenylamino) ethyl)
  • Particular embodiments of the invention are the method for promoting the penetration and its use, wherein TBEP is applied in the amounts (B) according to the invention with mixtures of herbicides and safener (A), either simultaneously or sequentially.
  • Preferred herbicide-safener mixtures are combinations of the following compounds with one another:
  • ACCase inhibitors such as alloxydim, butroxydim, clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofopmethyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop , Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfopetotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim, Tralkoxydim and isoxapyr
  • HPPD p-hydroxyphenyl pyruvate dioxygenase
  • d) compounds which act as safeners such as AD 67 (4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane), benoxacor, CL 304,415 (4-carboxymethylchroman-4-carboxylic acid), cloquintocet, Cloquintocet-mexyl, cyprosulfamides, dichloromide, dicyclonon, DKA-24 (N1, N2-diallyl-N2-dichloroacetylglycine amides), fenchlorazoles, fenchlorazoles-ethyl, fenclorim, flurazoles, fluxofenim, furilazoles, isoxadifen-ethyl, mefenpyr-diethyl, MW 191 ( 2-dichloromethyl-2-methyl-1,3-dioxolane),
  • Naphthalic anhydride naphthalene-1,8-dicarboxylic anhydride
  • oxabetrinil oxabetrinil
  • Tl-35 1-dichloroacetylazepane
  • herbicides are combined, e.g. Fenoxaprop-p-ethyl + loxyniloctanoate, diclofopmethyl + bromoxyniloctanoate, CMPP + bromoxyniloctanoate, MCPA + loxyniloctanoate, bromoxyniloctanoate + bromoxynil heptanoate, bromoxyniloctanoate + bromoxynilheptanoate + MCPA, bromoxynil octanoate + bromoxynil heptanoate + 2,4-D, phenmedipham + desmedipham, phenmedipham + desmedipham + ethofumesate, metamitron + ethofumesate, phenmedipham + ethofumesate + metamitron,
  • Cyprosulfamide Imazamox + Cyprosulfamide, Imazapic + Cyprosulfamide, Imazapyr + Cyprosulfamide, Imazethapyr + Cyprosulfamide, Mesosulfuron + Cyprosulfamide, Propoxycarbazone + Cyprosulfamide, Sulfosulfuron + Cyprosulfamide, Amidosulfuron + Cyprosulfamide, Chlorsulfuron + Cyprosulfamide, Imazaquin + Cyprosulfamide, Triasulfuron + Cyprosulfamide, Sulfometuron + Cyprosulfamide, cyclosulfamuron + cyprosulfamide, flupyrsulfuron + cyprosulfamide, pyrazosulfuron + cyprosulfamide, azimsulfuron + cyprosulfamide, bensulfuron + cyprosulfamide, bispyribac +
  • the weight ratio safener: herbicide 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, very particularly preferably from 1:10 to 10: 1
  • Herbicide (s) and safener (s) are usually dependent on the type of herbicide and / or the safener used and on the nature of the plant stock to be treated.
  • herbicides from the group of ACCase inhibitors such as alloxydim, butroxydim, clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop- P-ethyl, Fluazifop, Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfopetotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim,
  • the crop protection agents used in the process according to the invention generally contain from 0.01 to 99% by weight, in particular from 0.1 to 95% by weight, of the active compounds from the group of herbicides and / or safeners.
  • Tributoxyethyl phosphate (TBEP) as component (B) has the CAS Regno: 78-51-3 and is described in detail in this entry in the literature in its other properties.
  • the content of TBEP (B) in the pesticides used in the method according to the invention is dependent on the area-related application amount per hectare (ha) and must therefore be adjusted accordingly. This also applies to the preparation of an application solution, for example a spray mixture, when using the method according to the invention.
  • the area-related application rates for TBEP (B) are between 2.5 and 150 g / ha, preferably 5 to 100 g / ha, more preferably 10 to 100 g / ha, the volume of the spray mixture generally being between 100-500 L / ha lies.
  • component (C) in the preparation of Pesticides for the method according to the invention and / or the application according to the inventive method preferably in the form of spray mixtures, the addition of one or more emulsifiers may be necessary.
  • Suitable emulsifiers are from the group of ionic and nonionic emulsifiers and mixtures thereof with HLB values of 10 to 17 (eg emulsifier 1371B). They may be added either directly and / or by the formulation of components (A) and / or (B).
  • the surface-related application rates of component (C) are in the application of the plant protection agent according to the invention and / or the method according to the invention generally between 10 and 200 g / ha, preferably between 20 and 200 g / ha.
  • auxiliaries and additives (component D) 1 which may be present in the formulations according to the invention, preferably liquid formulations, all customary formulation auxiliaries are suitable, such as organic solvents, defoamers, emulsifiers other than component (C), dispersants, Preservatives, acids and bases, dyes, fillers and also water.
  • Suitable organic solvents are all customary organic solvents which readily dissolve the agrochemical active ingredients used.
  • Aliphatic and aromatic, optionally halogenated hydrocarbons such as toluene, xylene, Solvesso ®, vegetable and mineral oils, such as white spirit, kerosene, alkylbenzenes and spindle oil, furthermore propylene carbonate, carbon tetrachloride, chloroform, methylene chloride and methylene chloride, and also esters, such as ethyl acetate, Lactates furthermore lactones, such as butyrolactone, as well as lactams, such as N-methylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone N-octylcaprolactam and N-methylcaprolactam, ⁇ -butyrolactone, dimethylformamide and tributyl phosphate.
  • defoamers are common, in formulations of agrochemical Active substances existing defoamers in question.
  • examples include silicone oils, dispersions of silicone oils, magnesium stearate, phosphinic and phosphonic acids, in particular Fluowet PL 80 ® .
  • component (C) As of component (C) different emulsifiers are common, in
  • Formulations of agrochemical agents existing surface-active substances in question are ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols Fatty acid esters, end capped and non end capped alkoxylated linear and branched, saturated and unsaturated fatty acids, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, aryl sulfates, ethoxylated arylalkylphenols such as
  • Tristyrylphenol ethoxylate having an average of 16 ethylene oxide units per molecule, further ethoxylated and propoxylated arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxy and propoxylates.
  • Suitable dispersants are all substances customarily used in crop protection agents for this purpose.
  • preference is given to natural and synthetic water-soluble polymers such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, furthermore polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, ligninsulfonates, polymethacrylic acid and co-polymers.
  • Suitable dyes are all customary for the production of pesticides inorganic or organic dyes. Examples include titanium dioxide, carbon black, zinc oxide and blue pigments.
  • Suitable fillers are all substances normally used for this purpose in crop protection agents.
  • inorganic particles such as carbonates, silicates and oxides having an average particle size of 0.005 to 10 .mu.m, more preferably from 0.02 to 2 microns.
  • examples include silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates.
  • Suitable compounds which act as emulsion stabilizers and / or crystallization inhibitors are all substances conventionally used for this purpose in crop protection agents.
  • the content of the individual components in the crop protection agents used in the method according to the invention and the area-related application amount when using the method according to the invention can be varied within a substantial range.
  • formulation types are those mentioned in the "Manual on development and use of FAO and WHO specifications for pesticides" (FAO and WHO, 2002, appendix E) (each using the GCPF formulation codes with English abbreviation and designation): AL Any other liquid; AP Capsule Suspension; DC Powder Fbr dry seed treatment; EC Capsule Suspension; DC Dispersible concentrate; DC Powder;
  • Emulsifiable concentrate ED Electrochargeable liquid; EC Emulsifiable Granules; EO emulsion, water in oil; EP emulsifiable powder; ES Emulsion for seed treatment; EW emulsion, oil in water; FG fine granule; FS Flowable concentrate for seed treatment; GF Gel for Seed Treatment; GG Macrogranule; GL emulsifiable gel; GP flo-dust; GR Granule; GS Grease; GW Water soluble gel; HN Hot fogging concentrate; KK Combi-pack solid / liquid; KL Combi-pack liquid / liquid; KN CoId fogging concentrate; KP Combi-pack solid / solid; LA Lacquer; LS Solution for seed treatment; ME microemulsion; MG microgranules; OD OiI dispersi ⁇ n; Oxygen miscible flowable concentrate / oil miscible suspension; OL OiI miscible liquid; OP Oi
  • liquid formulation types Preference is given to liquid formulation types. These include the formulation types OD OiI dispersion; DC (dispersible concentrate GCPF formulation code); EC (GCPF Formulation Code for Emulsion Concentrate); EW (GCPF Formulation code for oil-in-water emulsion); ES (GCPF Formulation Code for Emulsion Stain); FS (GCPF Formulation Code for Multiphase Concentrate for Seed Treatment); EO (GCPF formulation code for water in oil emulsion); ME (GCPF Formulation Code for Microemulsion); SE (GCPF formulation code for suspoemulsion); SL (GCPF formulation code for water-soluble concentrate); CS (Capsule Suspension GCPF Formulation Code) and AL (GCPF Formulation Code for ready-to-use liquid formulation, other liquids for undiluted use).
  • DC disersible concentrate GCPF formulation code
  • EC GCPF Formulation Code for Emulsion Concentrate
  • EW GCPF Formulation code for oil-in-water emulsion
  • Oil dispersions are Especially preferred. Oil dispersion, formulation type OD), emulsion concentrates (formulation type EC).
  • the active ingredient concentration z. B. about 10 to 90 wt .-%; the remainder to 100% by weight consists of TBEP (B) and customary formulation constituents (emulsifier, auxiliaries and additives), which applies to all formulations.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the concentration of active ingredient may be about 1 to 50, preferably 3 to 30,% by weight.
  • the invention further relates to a method for controlling harmful organisms, preferably harmful plants, wherein the components used in the process according to the invention, preferably in an effective amount, is applied to the harmful plants.
  • the invention further relates to processes according to the invention containing at least the components (A) and (B), which in a preferred embodiment show superadditive effects (synergism). Due to the improved control of harmful organisms by the method according to the invention, it is possible to reduce the application rate and / or to increase the safety margin. Both are economically as well as ecologically sensible.
  • the choice of the amounts to be used by components (A) and (B) and the ratio of components (A): (B) are dependent on a whole series of factors.
  • Plant protection agent is e.g. in such a way that the components are mixed together in the desired ratios.
  • agrochemical active ingredients are solids, they are generally used either in finely ground form or in the form of a solution or suspension in an organic solvent or water. If the agrochemical active ingredient is liquid, the use of an organic solvent is often unnecessary. It is also possible to use a solid agrochemical active ingredient in the form of a melt.
  • the temperatures can be varied within a certain range when carrying out the process. It generally works at temperatures between 0 0 C and 80 0 C, preferably between 10 0 C and 60 0 C.
  • Plant protection agents are generally used by mixing TBEP (B) with one or more of the agrochemical active ingredients (A) and optionally with the emulsifier (C) and the auxiliary substances and additives (D).
  • the order in which the components are mixed together depends on the type of formulation.
  • customary devices are considered, which are used for the production of agrochemical formulations.
  • all forms of administration known to those skilled in the art may be used as application forms; Examples include: spraying, dipping, misting and a number of special processes for direct under- or above-ground treatment of whole plants or parts (seed, root, stolons, stems, stem, leaf), such as stem injection in trees or stem bandages in perennials , and a number of special indirect application methods.
  • the respective surface and / or object-related application rate of the crop protection agents of the most varied types of formulations used in the process according to the invention and of the process according to the invention for controlling said harmful organisms varies greatly.
  • the application media known to those skilled in the art as customary for the respective field of application are generally used in the customary amounts; for example, from several hundred liters of water per hectare in standard spraying over a few liters of oil per hectare in the "Ultra Low Volume"
  • concentrations of the crop protection agents used in the process according to the invention in the corresponding application media therefore vary widely and depend on the respective field of use. In general, concentrations are used which are known to the person skilled in the art as customary for the respective field of use. Preference is given to concentrations of from 0.01% by weight to 99% by weight, particularly preferably from 0.1% by weight to 90% by weight.
  • the application rate of the crop protection agents of the most varied formulation types used in the process according to the invention, as well as the components necessary for carrying out the process according to the invention, can be varied within a relatively wide range. It depends on the particular herbicides and / or safeners and their content in the formulations.
  • the TBEP (B) to be used is generally applied together with the active substance (A) or directly after one another, preferably in the form of a spray mixture containing TBEP (B) in inventive amounts and the active ingredient (s) in effective amounts and optionally one or more emulsifiers (C).
  • a spray mixture containing TBEP (B) in inventive amounts and the active ingredient (s) in effective amounts and optionally one or more emulsifiers (C).
  • other customary auxiliaries and additives can be added.
  • the spray mixture is preferably based on water and / or an oil, e.g. made of a high boiling hydrocarbon such as kerosene or paraffin.
  • the components for the process according to the invention can be realized either as a tank mixture or via a "ready-to-use formulation" (co-formulation).
  • the plants treated according to the invention are all types of harmful plants, such as weeds.
  • the application in economically important for example, transgenic crops of useful and ornamental plants, such as cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or even cultures of peanut, sugar beet , Cotton, soy, rapeseed, potato, tomato, pea and other vegetables are preferred.
  • the crop protection agents used in the process according to the invention, as well as the processes according to the invention have a number of advantages.
  • the general penetration of the active ingredients into the plant tissue by TBEP is significantly improved.
  • the faster onset of penetration thus also causes a higher rainfastness.
  • the penetration is improved at lower temperatures (for example less than 15 ° C.).
  • TBEP has been found to be more compatible than other alkyl ester additives in trials.
  • the use of TBEP thus allows savings on the active ingredients used.
  • TBEP is less harmful to the environment as it has a reduced volatility.
  • the penetration of drugs was measured by enzymatically isolated cuticle of apple tree leaves.
  • the cuticles represent all green parts of plants, such as leaf blade, petiole, stalk, stem, Hypocotyl and many fruits.
  • Sheets were used, which were cut in the fully developed state of apple trees of the variety Golden Delicious. The isolation of the cuticles took place in such a way that
  • the cuticles were placed with tweezers in the middle of the silicone grease-coated edges of the diffusion cells and sealed with a likewise greased ring.
  • the arrangement was chosen so that the morphological outside of the cuticles was directed outwards, ie towards the air, while the original inside side was facing the inside of the diffusion cell.
  • the diffusion cells were filled with water or with a mixture of water and solvent.
  • the TBEP according to the invention leads to an advantageously higher absorption increase of active substances than the penetration promoters of the prior art. This result is surprising and was not expected in view of the prior art.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of chemical plant protection, especially the use of a specific compound as a penetration enhancer for agrochemical active ingredients from the group of herbicides and safeners. The compound used is tributoxyethyl phosphate (TBEP).

Description

Beschreibung description
Penetrationsförderer für Herbizide und SafenerPenetration promoter for herbicides and safeners
Die Erfindung betrifft das Gebiet des chemischen Pflanzenschutzes, insbesondere die Verwendung einer speziellen Verbindung als Penetrationsförderer für agrochemische Wirkstoffe aus der Gruppe der Herbizide und Safener sowieThe invention relates to the field of chemical crop protection, in particular the use of a special compound as a penetration promoter for agrochemical active substances from the group of herbicides and safeners and
Pflanzenschutzmittel enthaltend diese Verbindung. Bei der Verbindung handelt es sich um Tributoxyethylphosphat (CAS Regno: 78-51-3; im folgenden als TBEP bezeichnet).Plant protection product containing this compound. The compound is tributoxyethyl phosphate (CAS Regno: 78-51-3, hereinafter referred to as TBEP).
Die Förderung der Penetration von Herbiziden und Safenern in Pflanzen wird durch 'Penetrationsförderer1 bewirkt. Unter dem Begriff Penetrationsförderer werden Verbindungen verstanden, welche die Aufnahme von Herbiziden und Safenern, allein oder in Mischung, durch die Kutikula einer Pflanze in die Pflanze fördern, d.h. die Aufnahmegeschwindigkeit beschleunigen und/oder die aufgenommene Menge des Wirkstoffs in die Pflanze erhöhen.The promotion of the penetration of herbicides and safeners into plants is effected by 'Penetrationsförderer 1 . The term penetration promoter is understood to mean compounds which promote the uptake of herbicides and safeners, alone or in a mixture, through the cuticle of a plant into the plant, ie accelerate the absorption rate and / or increase the absorbed amount of the active substance into the plant.
Stoffe, welche die Penetration von Herbiziden und/oder Safenern durch die Kutikula der Pflanze erhöhen sind wertvolle Hilfsstoffe im chemischen Pflanzenschutz. Verschiedene Stoffklassen sind als Penetrationsförderer bereits bekannt (siehe z.B. WO 2005/104844 A). DE 3513889 A1 behandelt allgemein Penetrationsförderer als "Aktivator" für Biozide und in EP 579052 A2 werden als Penetrationsförderer Verbindungen aus der Gruppe Alkylphosphate, wie Tributylphosphat und Tripropylphosphat, beschriebenen. Trotzdem besteht unter verschiedenen Gesichtspunkten immer noch ein Bedarf an weiteren Verbindungen mit vorteilhafteren Eigenschaften.Substances which increase the penetration of herbicides and / or safeners through the cuticle of the plant are valuable auxiliaries in chemical crop protection. Various classes of substances are already known as penetration enhancers (see for example WO 2005/104844 A). DE 3513889 A1 generally treats penetration promoters as "activators" for biocides and EP 579052 A2 describes compounds from the group of alkyl phosphates, such as tributyl phosphate and tripropyl phosphate, as penetration promoters. Nevertheless, there is still a need for further compounds with more advantageous properties from a variety of viewpoints.
Aufgabe der Erfindung ist es daher, weitere vorteilhafte Stoffe mit penetrationsfördernden Eigenschaften für agrochemische Wirkstoffe bereitzustellen. Es wurde nun überraschend gefunden, dass sich das Lösungsmittel TBEP im Gegensatz zu vielen anderen Lösungsmitteln in bestimmten niedrigeren Aufwandmengen und bestimmten Mischungsverhältnissen zum Wirkstoff zur Erhöhung der Penetration von Herbiziden und Safenem, allein oder in Mischung, durch die Kutikula der Pflanze und damit zur biologischen Wirkungssteigerung von Pflanzenschutzmitteln eignet.The object of the invention is therefore to provide further advantageous substances with penetration-promoting properties for agrochemical active ingredients. It has now surprisingly been found that the solvent TBEP, in contrast to many other solvents in certain lower application rates and certain mixing ratios to the active ingredient to increase the penetration of herbicides and safeners, alone or in mixture, by the cuticle of the plant and thus to increase biological activity of plant protection products.
TBEP ist schon als Lösungsmittel in entsprechend hohen Aufwandmengen im Pflanzenschutz bekannt, wie in Herbiziden (siehe z.B. WO 01/47356 A1 , EP 1251736 B1 , WO 00/56146 A1 , EP 1164842 B1 ) und Insektiziden (siehe z.B. JP 08291004 A, US 5674517 A). Aus GB 2022070 A ist TBEP bekannt zur Entblätterung, wobei es in Verhältnissen von (TBEP : Wirkstoff) 2 :1 bis 4 : 1 den zu herbiziden Wirkstoffen zugesetzt wurde. Auf dem Gebiet der Fungizide scheint die Verwendung von TBEP als Penetrationsförderer noch unbekannt zu sein.TBEP is already known as a solvent in correspondingly high application rates in crop protection, as in herbicides (see, for example, WO 01/47356 A1, EP 1251736 B1, WO 00/56146 A1, EP 1164842 B1) and insecticides (see, for example, JP 08291004 A, US 5674517 A). From GB 2022070 A TBEP is known for defoliation, wherein it was added in ratios of (TBEP: active ingredient) 2: 1 to 4: 1 to the herbicidal active ingredients. In the field of fungicides, the use of TBEP as a penetration promoter still seems to be unknown.
Gegenstand der Erfindung ist ein Verfahren zur Förderung der Penetration, wobei man die KomponentenThe invention relates to a method for promoting penetration, wherein the components
(A) einen oder mehrere Wirkstoffe aus der Gruppe der Herbizide und/oder Safener, (B) Tributoxyethylphosphat (TBEP) in Dosierungen von 2,5 bis 150,0 g/ha und (C) gegebenenfalls einen oder mehrere Emulgatoren, vorzugsweise aus der(A) one or more active substances from the group of herbicides and / or safeners, (B) tributoxyethyl phosphate (TBEP) in dosages of 2.5 to 150.0 g / ha and (C) optionally one or more emulsifiers, preferably from
Gruppe der ionischen und nicht-ionischen Emulgatoren und deren Gemische mit HLB-Werten von 10 bis 17, gleichzeitig oder sequentiell auf die Schadpflanzen appliziert.Group of ionic and nonionic emulsifiers and their mixtures with HLB values of 10 to 17, applied simultaneously or sequentially to the harmful plants.
Ebenso Gegenstand der Erfindung ist die Verwendung des hier beschriebenen Verfahrens, wobei man die Komponenten gleichzeitig oder sequentiell auf die Schadpflanzen appliziert.The invention likewise relates to the use of the method described here, wherein the components are applied simultaneously or sequentially to the harmful plants.
Da der Wirkmechanismus von TBEP als Penetrationsförderer grundsätzlich unabhängig von der Art des eingesetzten agrochemischen Wirkstoffs ist, kommen alle Wirkstoffe aus der Gruppe der Herbizide in Frage, deren biologische Wirksamkeit gegen Unkäuter im weiteren Sinne, im folgenden als Schadpflanzen bezeichnet, durch erhöhtes Eindringen in die Schadpflanze gesteigert werden kann. In Falle der Wirkstoffe aus der Gruppe der Safener wird ein erhöhtes Eindringen in die Kulturpflanze gewünscht, damit die Schutzwirkung gesteigert werden kann.Since the mechanism of action of TBEP as a penetration promoter is fundamentally independent of the type of agrochemical active ingredient used, all active substances from the group of herbicides come into question whose biological Activity against weeds in the broader sense, hereinafter referred to as harmful plants, can be increased by increased penetration into the harmful plant. In the case of the active ingredients from the group of safeners, an increased penetration into the cultivated plant is desired so that the protective effect can be increased.
Vorzugsweise genannt seien Wirkstoffe aus der Gruppe der Herbizide, umfassend auch Pflanzenwuchsregulatoren, und aus der Gruppe der Safener, sowie Pflanzennährstoffe, die über systemische Eigenschaften verfügen, sowie als Kombinationspartner in Frage kommende Kontaktmittel. Im folgenden beinhaltet der Begriff Herbizide sowohl Herbizide wie auch Pflanzenwuchsregulatoren soweit aus dem Zusammenhang nichts anderes hervorgeht.Preferably mentioned are active compounds from the group of herbicides, including plant growth regulators, and from the group of safeners, as well as plant nutrients which have systemic properties, and as a combination partner candidate contact agents. In the following, the term herbicides includes both herbicides and plant growth regulators unless the context otherwise indicates.
Weiterhin bevorzugt innerhalb der oben genannten Gruppen sind systemische Wirkstoffe, d.h. solche die von der Pflanze durch die Blätter oder über die Wurzeln aufgenommen und im Saftstrom, dem Transportsystem oder Pflanze, weitergeleitet werden. Besonders bevorzugt sind solche Wirkstoffe, die einen Log P Wert von ≤4 aufweisen (bestimmt gemäß EEC-Directive 79/831 Annex V. A8 durch HPLC, Gradientenmethode, Acetronitril / 0,1 % wässrige Phosphorsäure), insbesondere solche mit einem Log P Wert von <4 und >0,1.Further preferred within the above groups are systemic agents, i. those that are absorbed by the plant through the leaves or over the roots and passed on in the juice stream, the transport system or plant. Particular preference is given to those active compounds which have a Log P value of ≦ 4 (determined according to EEC Directive 79/831 Annex V. A8 by HPLC, gradient method, acetonitrile / 0.1% aqueous phosphoric acid), in particular those having a Log P value of <4 and> 0.1.
Beispiele für einzelne Wirkstoffe aus der Gruppe der Herbizide, umfassend auch Pflanzenwuchsregulatoren, und aus der Gruppe der Safener sind:Examples of individual active substances from the group of herbicides, including plant growth regulators, and from the group of safeners are:
Herbizideherbicides
Beispiele für Herbizide sind z.B. ALS-Inhibitoren (Acetolactat-Synthetase-Inhibitoren) oder Herbizide aus der Gruppe der Carbamate, Thiocarbamate, Halogenacetanilide, substituierte Phenoxy-, Naphthoxy- und Phenoxyphenoxycarbonsäure-Derivate sowie Heteroaryloxy-phenoxyalkancarbonsäure-Derivate, wie Chinolyloxy-, Chinoxalyl-oxy-, Pyridyloxy-, Benzoxazolyloxy- und Benzthiazolyloxyphenoxyalkan- carbonsäureester, Cyclo-hexandionabkömmlinge, Imidazolinone, Phosphor-haltige Herbizide, z.B. vom Glufosinate-Typ oder vom Glyphosate-Typ, Pyrimidinyloxy- pyridincarbonsäure-Derivate, Pyrimidyloxy-benzoesäure-Derivate, Triazolo- pyrimidin-sulfonamid-Derivate sowie S-(N-Aryl-N-alkylcarbamoylmethyl)- dithiophosphorsäureester, Harnstoffe sowie Hydroxybenzonitrile.Examples of herbicides are, for example, ALS inhibitors (acetolactate synthetase inhibitors) or herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and heteroaryloxy-phenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyl oxy-, pyridyloxy-, benzoxazolyloxy- and benzthiazolyloxyphenoxyalkane-carboxylic acid esters, cyclohexanedione derivatives, imidazolinones, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, pyrimidinyloxy pyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidine-sulfonamide derivatives and S- (N-aryl-N-alkylcarbamoylmethyl) -dithiophosphoric acid esters, ureas and hydroxybenzonitriles.
Bei den herbiziden Wirkstoffen aus der Gruppe der ALS-Inhibitoren wieIn the herbicidal active ingredients from the group of ALS inhibitors such
Sulfonylharnstoffe sind im Sinne der vorliegenden Erfindung neben den neutralen Verbindungen stets auch deren Salze mit anorganischen und/oder organischen Gegenionen zu verstehen. So können z.B. Sulfonylharnstoffe z.B. Salze bilden, bei denen der Wasserstoff der -SO2-NH-Gruppe durch ein für die Landwirtschaft geeignetes Kation ersetzt ist. Diese Salze sind beispielsweise Metallsalze, insbesondere Alkalimetallsalze oder Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, oder auch Ammoniumsalze oder Salze mit organischen Aminen. Ebenso kann Salzbildung durch Anlagerung einer Säure an basischen Gruppen, wie z.B. Amino und Alkylamino, erfolgen. Geeignete Säuren hierfür sind starke anorganische und organische Säuren, beispielsweise HCl, HBr, H2SO4 oder HNO3.For the purposes of the present invention, sulphonylureas are always to be understood as meaning, in addition to the neutral compounds, their salts with inorganic and / or organic counterions. Thus, for example, sulfonylureas can form, for example, 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 else ammonium salts or salts with organic amines. Likewise, salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
A) Bevorzugte ALS-Inhibitoren entstammen aus der Reihe der Sulfonylharnstoffe und/oder ihrer Salze, z.B. Pyrimidin- oder Triazinylaminocarbonyl- [benzol-, pyridin-, pyrazol-, thiophen- und (alkylsulfonyl)-alkylamino-]-sulfamide. Solche geeigneten Sulfonylharnstoffe sind beispielsweiseA) Preferred ALS inhibitors are derived from the series of sulfonylureas and / or their salts, e.g. Pyrimidine or triazinylaminocarbonyl [benzene, pyridine, pyrazole, thiophene and (alkylsulfonyl) alkylamino] sulfamides. Such suitable sulfonylureas are, for example
A1) Phenyl- und Benzylsulfonylharnstoffe und verwandte Verbindungen, z.B.A1) phenyl and benzylsulfonylureas and related compounds, e.g.
1-(2-Chlθφhenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)-harnstoff1- (2-Chloro-phenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea
(Chlorsulfuron), 1-(2-Ethoxycarbonylphenylsulfonyl)-3-(4-chlor-6-methoxypyrimidin-2-yl)-harnstoff(Chlorosulfuron), 1- (2-ethoxycarbonylphenylsulfonyl) -3- (4-chloro-6-methoxypyrimidin-2-yl) -urea
(Chlorimuron-ethyl),(Chlorimuron-ethyl),
1-(2-Methoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)-harnstoff1- (2-methoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea
(Metsulfuron-methyl),(Metsulfuron-methyl),
1-(2-Chlorethoxyphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)-harnstoff (Triasulfuron),1- (2-chloroethoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea (triasulfuron),
1-(2-Methoxycarbonylphenylsulfonyl)-3-(4,6-dimethylpyrimidin-2-yl)-harnstoff1- (2-Methoxycarbonylphenylsulfonyl) -3- (4,6-dimethylpyrimidin-2-yl) -urea
(Sulfumeturon-methyl), 1-(2-Methoxycarbonylphenylsulfonyl)-3-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)-3- methylhamstoff (Tribenuron-methyl),(Sulfumeturon-methyl), 1- (2-Methoxycarbonylphenylsulfonyl) -3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) -3-methylurea (tribenuron-methyl),
1-(2-Methoxycarbonylbenzylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)-harnstoff1- (2-Methoxycarbonylbenzylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) -urea
(Bensulfuron-methyl), 1-(2-Methoxycarbonylphenylsulfonyl)-3-(4,6-bis-(difluoirnethoxy)pyrirnidin-2-yl)- harnstoff, (Primisulfuron-methyl),(Bensulfuron-methyl), 1- (2-Methoxycarbonylphenylsulfonyl) -3- (4,6-bis (difluoro-methoxy) pyrirnidin-2-yl) -urea, (Primisulfuron-methyl),
3-(4-Ethyl-6-methoxy-1 ,3,5-triazin-2-yl)-1 -(2,3-dihydro-1 ,1 -dioxo-2-methylbenzo-3- (4-Ethyl-6-methoxy-1,3,5-triazin-2-yl) -1- (2,3-dihydro-1,1-dioxo-2-methylbenzoyl)
[b]thiophen-7-sulfonyl)-harnstoff (EP-A 0 079 683),[b] thiophene-7-sulfonyl) urea (EP-A 0 079 683),
3-(4-Ethoxy-6-ethyl-1 ,3)5-triazin-2-yl)-1-(2,3-dihydro-1 ,1-dioxo-2-methylbenzo[b]- thiophen-7-sulfonyl)harnstoff (EP-A 0 079 683),3- (4-ethoxy-6-ethyl-1, 3) 5-triazin-2-yl) -1- (2,3-dihydro-1, 1-dioxo-2-methylbenzo [b] - thiophen-7- sulfonyl) urea (EP-A 0 079 683),
3-(4-Methoxy-6-methyl-1 ,3,5-triazin-2-yl)-1-(2-methoxycarbonyl-5-jod-phenyl- sulfonyl)-harnstoff (lodosulfuron-methyl und dessen Natriumsalz, WO 92/13845),3- (4-Methoxy-6-methyl-1,3,5-triazin-2-yl) -1- (2-methoxycarbonyl-5-iodo-phenylsulfonyl) -urea (iodosulfuron-methyl and its sodium salt, WO 92/13845)
DPX-66037, Triflusulfuron-methyl (s. Brighton Crop Prot. Conf. - Weeds - 1995, S.DPX-66037, triflusulfuron-methyl (see Brighton Crop Prot. Conf. - Weeds - 1995, p.
853), CGA-277476, (s. Brighton Crop Prot. Conf. - Weeds - 1995, S. 79),853), CGA-277476, (see Brighton Crop Prot. Conf. - Weeds - 1995, p.
Methyl-2-[3-(4>6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methansulfon-amido- methyl-benzoat (Mesosulfuron-methyl, WO 95/10507),Methyl 2- [3- (4- > 6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-methanesulfonamido-methyl benzoate (mesosulfuron-methyl, WO 95/10507),
N,N-Dimethyl-2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-forrnylamino- benzamid (Foramsulfuron, WO 95/01344);N, N-dimethyl-2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-forrnylaminobenzamide (foramsulfuron, WO 95/01344);
A2) Thienylsulfonylharnstoffe, z.B.A2) Thienylsulfonylureas, e.g.
1-(2-Methoxycarbonylthiophen-3-yl)-3-(4-methoxy-6-methyM ,3,5-triazin-2- yl)harnstoff (Thifensulfuron-methyl);1- (2-methoxycarbonylthiophen-3-yl) -3- (4-methoxy-6-methyl, 3,5-triazin-2-yl) urea (thifensulfuron-methyl);
A3) Pyrazolylsulfonylharnstoffe, z.B.A3) pyrazolylsulfonylureas, e.g.
1-(4-Ethoxycarbonyl-1-methylpyrazol-5-yl-sulfonyl)-3-(4,6-dimethoxypyrimidin-2- yl)harnstoff (Pyrazosulfuron-methyl);1- (4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (pyrazosulfuron-methyl);
Methyl-3-chlor-5-(4,6-dimethoxypyrirnidin-2-ylcarbamoylsulfamoyl)-1-methyl-pyrazol-Methyl 3-chloro-5- (4,6-dimethoxypyrirnidin-2-ylcarbamoylsulfamoyl) -1-methyl-pyrazole
4-carboxylat (EP-A 0 282 613); 5-(4,6-Dimethylpyrimidin-2-yl-carbamoylsulfamoyl)-1-(2-pyridyl)-pyrazol-4-car- bonsäuremethylester (NC-330, s. Brighton Crop Prot. Conference 'Weeds' 1991 , Vol.4-carboxylate (EP-A 0 282 613); Methyl 5- (4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl) -1- (2-pyridyl) pyrazole-4-carboxylic acid (NC-330, see Brighton Crop Prot. Conference 'Weeds' 1991, Vol.
1 , S. 45 ff.), DPX-A8947, Azimsulfuron, (s. Brighton Crop Prot. Conf. Weeds1 1995, S. 65);1, p. 45 ff.), DPX-A8947, azimsulfuron, (see Brighton Crop Prot. Conf. Weeds 1 1995, p.
A4) Sulfondiamid-Derivate, z.B.A4) sulfone diamide derivatives, e.g.
3-(4,6-Dimethoxypyrimidin-2-yl)-1-(N-methyl-N-methylsulfonylaminosulfonyl)- harnstoff (Amidosulfuron) und dessen Strukturanaloge (EP-A 0 131 258 und Z. PfI. Krankh. PfI. Schutz, Sonderheft XII, 489-497 (1990));3- (4,6-dimethoxypyrimidin-2-yl) -1- (N-methyl-N-methylsulfonylaminosulfonyl) urea (amidosulfuron) and its structural analogs (EP-A-0 131 258 and Z. Pfi. Ill. PfI Special Edition XII, 489-497 (1990));
A5) Pyridylsulfonylharnstoffe, z.B.A5) pyridylsulfonylureas, e.g.
1-(3-N,N-Dimethylaminocarbonylpyridin-2-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2- yl)-harnstoff (Nicosulfuron),1- (3-N, N-dimethylaminocarbonylpyridin-2-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (nicosulfuron),
1-(3-Ethylsulfonylpyridin-2-ylsulfonyl)-3-(-(4,6-dimethoxypyrimidin-2-yl)-hamstoff1- (3-Ethylsulfonylpyridin-2-ylsulfonyl) -3 - (- (4,6-dimethoxypyrimidin-2-yl) -hamstoff
(Rimsulfuron),(Rimsulfuron),
2-[3-(4,6-Dimethoxypyrimidin-2-yl)-ureidosulfonyl]-6-trifluormethyl-3-pyridin- carbonsäuremethylester, Natriumsalz (DPX-KE 459, Flupyrsulfuron, s. Brighton Crop Prot. Conf. Weeds, 1995, S. 49),Methyl 2- [3- (4,6-dimethoxypyrimidin-2-yl) -uridosulfonyl] -6-trifluoromethyl-3-pyridinecarboxylate, sodium salt (DPX-KE 459, flupyrsulfuron, see Brighton Crop Prot. Conf., Weeds, 1995 , P. 49),
Pyridylsulfonylharnstoffe, wie sie z.B. in DE-A 40 00 503 und DE-A 40 30 577 beschrieben sind, vorzugsweise solche der FormelPyridylsulfonylureas, as e.g. in DE-A 40 00 503 and DE-A 40 30 577 are described, preferably those of the formula
worinwherein
E CH oder N, vorzugsweise CH, R20 lod oder NR25R26,E is CH or N, preferably CH, R 20 is iodine or NR 25 R 26 ,
R21 Wasserstoff, Halogen, Cyano, (CrC3)-Alkyl, (C1-Ca)-AIkOXy, (C1-C3)- Halogenalkyl, (Ci-C3)-Halogenalkoxy, (CrC3)-Alkylthio, (CrC3)-Alkoxy-(d-R 21 is hydrogen, halogen, cyano, (C r C 3 ) -alkyl, (C 1 -Ca) -alkoxy, (C 1 -C 3 ) -haloalkyl, (C 1 -C 3 ) -haloalkoxy, (C r C 3 ) -Alkylthio, (CrC 3 ) -alkoxy- (d-)
C3)-alkyl, (CrC3)-Alkoxy-carbonyl, Mono- oder Di-((CrC3)-alkyl)-amino, (C1- C3)-Alkylsulfinyl oder -sulfonyl, SO2-NRxRy oder CO-NRxRy, insbesondere Wasserstoff, Rx, Ry unabhängig voneinander Wasserstoff, (CrC3)-Alkyl, (Ci-C3)-Alkenyl, (C1-C3)- Alkinyl oder zusammen -(CH2)4-, -(CH2)S- oder -(CH2)2-O-(CH2)2-, n 0,1 ,2 oder 3, vorzugsweise 0 oder 1 ist,C 3 ) alkyl, (CrC 3 ) alkoxycarbonyl, mono- or di- ((CrC 3 ) alkyl) amino, (C 1 -C 3 ) alkylsulfinyl or sulfonyl, SO 2 -NR x R y or CO-NR x R y , in particular hydrogen, R x, R y are independently hydrogen, (C r C 3) alkyl, (Ci-C 3) -alkenyl, (C 1 -C 3) - alkynyl or together are - (CH 2) 4 -, - (CH 2 ) Is S- or - (CH 2 ) 2 -O- (CH 2 ) 2, n is 0.1, 2 or 3, preferably 0 or 1,
R22 Wasserstoff oder CH3, R23 Halogen, (CrC2)-Alkyl, (d-C2)-Alkoxy, (CrC2)-Halogenalkyl, insbesondere CF3, (CrC2)-Halogenalkoxy, vorzugsweise OCHF2 oder OCH2CF3,R 22 is hydrogen or CH 3, R 23 is halogen, (C r C 2) alkyl, (dC 2) alkoxy, (CrC 2) -haloalkyl, in particular CF3, (CrC 2) -haloalkoxy, preferably OCHF2 or OCH 2 CF 3 ,
R24 (CrC2)-Alkyl, (CrC2)-Halogenalkoxy, vorzugsweise OCHF2, oder (C1-C2)- Alkoxy,R 24 (-C 2) alkyl, (CrC 2) -haloalkoxy, preferably OCHF2, or (C 1 -C 2) - alkoxy,
R25 (CrC4)-Alkyl, R26 (CrC4)-Alkylsulfonyl oderR 25 (C r C 4 ) alkyl, R 26 (C r C 4 ) alkylsulfonyl or
R25 und R26 gemeinsam eine Kette der Formel -(CH2)3SO2- oder -(CH2)4SO2- bedeuten, z.B. 3-(4,6-Dimethoxypyrimiden-2-yl)-1-(3-N-methylsulfonyl-N-methyl- aminopyridin-2-yl)-sulfonylharnstoff, oder deren Salze;R 25 and R 26 together represent a chain of the formula - (CH 2 ) 3 SO 2 - or - (CH 2 ) 4 SO 2 -, for example 3- (4,6-dimethoxypyrimiden-2-yl) -1- (3 -N-methylsulfonyl-N-methyl-aminopyridin-2-yl) -sulfonylurea, or salts thereof;
A6) Alkoxyphenoxysulfonylharnstoffe, wie sie z.B. in EP-A 0 342 569 beschrieben sind, vorzugsweise solche der FormelA6) Alkoxyphenoxysulfonylureas, as described e.g. in EP-A 0 342 569, preferably those of the formula
worin E CH oder N, vorzugsweise CH, where E is CH or N, preferably CH,
R27 Ethoxy, Propoxy oder Isopropoxy, R28 Halogen, NO2, CF3, CN, (CrC4)-Alkyl, (CrC4)-Alkoxy, (CrC4)-Alkylthio oderR 27 is ethoxy, propoxy or isopropoxy, R 28 is halogen, NO 2, CF 3, CN, (C r C4) alkyl, (C r C4) alkoxy, (C r C4) alkylthio or
(C-ι-C3)-Alkoxy-carbonyl, vorzugsweise in 6-Position am Phenylring, n 0, 1 , 2 oder 3, vorzugsweise 0 oder 1 , R29 Wasserstoff, (d-C4)-Alkyl oder (C3-C4)-Alkenyl,(C 1 -C 3 ) -alkoxycarbonyl, preferably in the 6-position on the phenyl ring, n is 0, 1, 2 or 3, preferably 0 or 1, R 29 is hydrogen, (C 1 -C 4 ) -alkyl or (C 3 -) C 4 ) alkenyl,
R30, R31 unabhängig voneinander Halogen, (CrC2)-Alkyl, (CrC2)-Alkoxy, (C1-C2)- Halogenalkyl, (d-C2)-Halogenalkoxy oder (CrC2)-Alkoxy-(CrC2)-alkyl, vorzugsweise OCH3 oder CH3, bedeuten, z.B. 3-(4,6-Dimethoxypyrimidin-2- yl)-1-(2-ethoxyphenoxy)-sulfonylharnstoff, oder deren Salze;R 30, R 31 are independently halogen, (CrC 2) alkyl, (CrC 2) alkoxy, (C 1 -C 2) - haloalkyl, (dC 2) -haloalkoxy or (CrC 2) alkoxy (CrC 2 ) alkyl, preferably OCH 3 or CH 3 , for example 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea, or salts thereof;
A7) Imidazolylsulfonylhamstoffe, z.B. MON 37500, Sulfosulfuron (s. Brighton Crop Prot. Conf. Weeds1, 1995, S: 57), und andere verwandte Sulfonylharnstoff-Derivate und Mischungen daraus;A7) imidazolylsulfonylureas, eg MON 37500, sulfosulfuron (see Brighton Crop Prot. Conf., Weeds 1 , 1995, p. 57), and other related sulfonylurea derivatives and mixtures thereof;
Typische Vertreter dieser Wirkstoffe sind unter anderem die nachfolgend aufgeführten Verbindungen: Amidosulfuron, Azimsulfuron, Bensulfuron-Methyl, Chlorimuron-Ethyl, Chlorsulfuron, Cinosulfuron, Cyclosulfamuron, Ethametsulfuron- Methyl, Ethoxysulfuron, Flazasulfuron, Flupyrsulfuron-Methyl-Natrium, Halosulfuron- Methyl, Imazosulfuron, Metsulfuron-Methyl, Nicosulfuron, Oxasulfuron, Primisulfuron-Methyl, Prosulfuron, Pyrazosulfuron-Ethyl, Rimsulfuron, Sulfometuron- Methyl, Sulfosulfuron, Thifensulfuron-Methyl, Triasulfuron, Tribenuron-Methyl, Triflusulfuron-Methyl, lodosulfuron-Methyl und dessen Natriumsalz (WO 92/13845), Mesosulfuron-Methyl und dessen Natriumsalz (Agrow Nr. 347, 3. März 2000, Seite 22 (PJB Publications Ltd. 2000)) und Foramsulfuron und dessen Natriumsalz (Agrow Nr. 338, 15. Oktober 1999, Seite 26 (PJB Publications Ltd..2000)).Typical representatives of these active ingredients include the following compounds: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl-sodium, halosulfuron-methyl, imazosulfuron, Metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, iodosulfuron-methyl and its sodium salt (WO 92 / 13845), mesosulfuron-methyl and its sodium salt (Agrow No. 347, March 3, 2000, page 22 (PJB Publications Ltd. 2000)) and foramsulfuron and its sodium salt (Agrow No. 338, Oct. 15, 1999, page 26 (PJB Publications Ltd. 2000)).
B) Herbizide vom Typ der Phenoxyphenoxy- undB) Phenoxyphenoxy- and herbicides of the type phenoxyphenoxy
Heteroaryloxyphenoxycarbonsäure-Derivate, wieHeteroaryloxyphenoxycarboxylic acid derivatives, such as
B1 ) Phenoxyphenoxy- und Benzyloxyphenoxy-carbonsäure-Derivate, z.B. 2-(4-B1) phenoxyphenoxy- and benzyloxyphenoxy-carboxylic acid derivatives, e.g. 2- (4-
(2,4-Dichlorphenoxy)-phenoxy)-propionsäuremethylester (Diclofop-methyl),(2,4-dichlorophenoxy) -phenoxy) -propionic acid methyl ester (diclofop-methyl),
2-(4-(4-Brom-2-chlorphenoxy)-phenoxy)-propionsäuremethylester (DE-A 26 01 548), 2-(4-(4-Brom-2-fluoφhenoxy)-phenoxy)-propionsäuremethylester (US-A 4,808,750),2- (4- (4-bromo-2-chlorophenoxy) -phenoxy) -propionic acid methyl ester (DE-A 26 01 548), 2- (4- (4-bromo-2-fluoro-phenoxy) -phenoxy) -propionic acid methyl ester (US Pat. A 4,808,750),
2-(4-(2-Chlor-4-trifluormethylphenoxy)-phenoxy)-propionsäuremethylester (DE-A 242- (4- (2-chloro-4-trifluoromethylphenoxy) -phenoxy) -propionic acid methyl ester (DE-A 24
33067),33067)
2-(4-(2-Fluor-4-trifluormethylphenoxy)-phenoxy)-propionsäuremethylester (US-A2- (4- (2-Fluoro-4-trifluoromethylphenoxy) -phenoxy) -propionic acid methyl ester (US Pat
4,808,750), 2-(4-(2,4-Dichlorbenzyl)-phenoxy)-propionsäuremethylester (DE-A 24 17 487),4,808,750), 2- (4- (2,4-dichlorobenzyl) phenoxy) -propionic acid methyl ester (DE-A 24 17 487),
4-(4-(4-Trifluormethylphenoxy)-phenoxy)-pent-2-en-säureethylester, 2-(4-(4-Trifluormethylphenoxy)-phenoxy)-propionsäuremethylester (DE-A 24 33 067);4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-en-oate, 2- (4- (4-trifluoromethylphenoxy) -phenoxy) -propionic acid methyl ester (DE-A 24 33 067);
B2) "Einkernige" Heteroaryloxyphenoxy-alkancarbonsäure-Derivate, z.B. 2-(4-(3,5-Dichlθφyridyl-2-oxy)-phenoxy)-propionsäureethylester (EP-A 0 002 925),B2) "mononuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, e.g. 2- (4- (3,5-dichloropyridyl-2-oxy) -phenoxy) -propionic acid ethyl ester (EP-A 0 002 925),
2-(4-(3,5-Dichloφyridyl-2-oxy)-phenoxy)-propionsäurepropargylester2- (4- (3,5-Dichloφyridyl-2-oxy) phenoxy) -propionsäurepropargylester
(EP-A 0 003 114),(EP-A 0 003 114),
2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)-phenoxy)-propionsäuremethylester2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate
(EP-A 0 003 890), 2-(4-(3-Chlor-5-trifluormethyl-2-pyridyloxy)-phenoxy)-propionsäureethylester(EP-A 0 003 890), ethyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate
(EP-A 0 003890),(EP-A 0 003 890),
2-(4-(5-Chlor-3-fluor-2-pyridyloxy)-phenoxy)-propionsäurepropargylester2- (4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy) -propionsäurepropargylester
(EP-A O 191 736),(EP-A 0 191 736),
2-(4-(5-Trifluormethyl-2-pyridyloxy)-phenoxy)-propionsäurebutylester (Fluazifop-butyl);Butyl 2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) -propionate (fluazifop-butyl);
B3) "Zweikernige" Heteroaryloxyphenoxy-alkancarbonsäure-Derivate, z.B.B3) "binuclear" heteroaryloxyphenoxy-alkanecarboxylic acid derivatives, e.g.
2-(4-(6-Chlor-2-chinoxalyloxy)-phenoxy)-propionsäuremethylester und -ethylester2- (4- (6-chloro-2-quinoxalyloxy) -phenoxy) -propionic acid methyl ester and ethyl ester
(Quizalofopmethyl und Quizalofopethyl), 2-(4-(6-Fluor-2-chinoxalyloxy)-phenoxy)-propionsäuremethylester (s. J. Pest. Sei.(Quizalofopmethyl and quizalofopethyl), 2- (4- (6-fluoro-2-quinoxalyloxy) -phenoxy) -propionic acid methyl ester (see J. Pest.
Vol. 10, 61 (1985)),Vol. 10, 61 (1985)),
2-(4-(6-Chlor-2-chinoxalyloxy)-phenoxy)-propionsäure-2-isopropylidenaminooxy- ethylester (Propaquizafop),2- (4- (6-chloro-2-quinoxalyloxy) -phenoxy) -propionic acid 2-isopropylideneaminooxyethyl ester (propaquizafop),
2-(4-(6-Chlorbenzoxazol-2-yl-oxy)-phenoxy)-propionsäureethylester (Fenoxaprop- ethyl), dessen D(+) Isomer (Fenoxaprop-P-ethyl) und 2-(4-(6-Chlorbenzthiazol-2- yloxy)-phenoxy)-propionsäureethylester (DE-A 26 40 730),2- (4- (6-chlorobenzoxazol-2-yl-oxy) -phenoxy) -propionic acid ethyl ester (fenoxapropethyl), its D (+) isomer (fenoxaprop-P-ethyl) and 2- (4- (6-chlorobenzthiazole -2-yloxy) -phenoxy) -propionic acid ethyl ester (DE-A 26 40 730),
2-(4-(6-Chlorchinoxalyloxy)-phenoxy)-propionsäure-tetrahydro-2-furylmethylester2- (4- (6-Chlorchinoxalyloxy) phenoxy) propionic acid-tetrahydro-2-furylmethylester
(EP-A 0 323 727);(EP-A 0 323 727);
C) Chloracetanilide, z.B.C) Chloroacetanilides, e.g.
N-Methoxymethyl-2,6-diethyl-chloracetanilid (Alachlor), N-(3-Methoxyprop-2-yl)-2-methyl-6-ethyl-chloracetanilid (Metolachlor), NKS-Methyl-i ^^-oxadiazol-δ-yl-methyO-chloressigsäure^.e-dimethylanilid, N-(2,6-Dimethylphenyl)-N-(1-pyrazolylmethyl)-chloressigsäureamid (Metazachlor);N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), NKS-methyl-1-oxadiazol-6-yl-methoxy-chloroacetic acid, 1-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolylmethyl) -chloroacetic acid amide (metazachlor);
D) Thiocarbamate, z.B. S-Ethyl-N.N-dipropylthiocarbamat (EPTC), S-Ethyl-N,N-diisobutylthiocarbamat (Butylate);D) thiocarbamates, e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylate);
E) Cyclohexandionoxime, z.B. 3-(1-Allyloxyiminobutyl)-4-hydroxy-6,6-dimethyl-2-oxOcyclohex-3-encarbon- säuremethylester, (Alloxydim),E) cyclohexanedione oximes, e.g. 3- (1-Allyloxyiminobutyl) -4-hydroxy-6,6-dimethyl-2-oxo-cyclohex-3-encarboxylic acid methyl ester, (alloxydim),
2-(1-Ethoxyiminobutyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1-on2- (1-Ethoxyiminobutyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one
(Sethoxydim),(Sethoxydim),
2-(1-Ethoxyiminobutyl)-5-(2-phenylthiopropyl)-3-hydroxy-cyclohex-2-en-1-on2- (1-Ethoxyiminobutyl) -5- (2-phenylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one
(Cloproxydim), 2-(1 -(3-Chlorallyloxy)-iminobutyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1 - on,(Cloproxydim), 2- (1- (3-chloroallyloxy) -iminobutyl) -5- (2-ethylthiopropyl) -3-hydroxycyclohex-2-en-1-one,
2-(1-(3-Chlorallyloxy)-iminopropyl)-5-(2-ethylthiopropyl)-3-hydroxy-cyclohex-2-en-1- on (Clethodim),2- (1- (3-chloroallyloxy) -iminopropyl) -5- (2-ethylthiopropyl) -3-hydroxycyclohex-2-en-1-one (clethodim),
2-(1-Ethoxyiminobutyl)-3-hydroxy-5-(thian-3-yl)-cyclohex-2-en-on (Cycloxydim), 2-(1 -Ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxy-cyclohex-2-en-1 -on2- (1-ethoxyiminobutyl) -3-hydroxy-5- (thian-3-yl) -cyclohex-2-enone (cycloxydim), 2- (1-ethoxyiminopropyl) -5- (2,4,6- trimethylphenyl) -3-hydroxy-cyclohex-2-en-1-one
(Tralkoxydim);(Tralkoxydim);
F) Imidazolinone, z.B. 2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methylbenzoesäure-methylester und 2-(4-lsopropyI-4-methyl-5-oxo-2-imidazolin-2-yl)-4-methylbenzoesäureF) imidazolinones, e.g. Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-imidazoline-2 yl) -4-methylbenzoic
(Imazamethabenz),(Imazamethabenz),
5-Ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid
(Imazethapyr),(Imazethapyr),
2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-chinolin-3-carbonsäure (lmazaquin), 2-(4-lsopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure (lmazapyr),2- (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -quinoline-3-carboxylic acid (imazaquin), 2- (4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl) -pyridine-3-carboxylic acid (imazapyr),
5-IVIethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-pyridin-3-carbonsäure5-IVIethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid
(Imazethamethapyr); G) Triazolopyrimidinsulfonamid-Derivate, z.B. N-(2,6-Difluorphenyl)-7-methyl-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2-sulfonamid (Flumetsulam), N-(2,6-Dichlor-3-methylphenyl)-5,7-dimethoxy-1 ,2,4-triazolo[1 ,5-c]pyrimidin-2- sulfonamid,(Imazethamethapyr); G) Triazolopyrimidinesulfonamide derivatives, eg N- (2,6-difluorophenyl) -7-methyl-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (flumetsulam), N- (2,6 Dichloro-3-methylphenyl) -5,7-dimethoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide,
N-(2,6-Difluorphenyl)-7-fluor-5-methoxy-1 ,2,4-triazolo[1 ,5-c]-pyrimidin-2-sulfonamid, N^.δ-Dichlor-S-methylphenyO-Z-chlor-δ-methoxy-I ^Λ-triazolofi .δ-cl-pyrimidin^- Sulfonamid, N-(2-Chlor-6-methoxycarbonyl)-5,7-dimethyl-1 ,2,4-triazolo[1 ,5-c]-pyrimidin-2- sulfonamid (EP-A 0 343 752, US-A 4,988,812);N- (2,6-Difluorophenyl) -7-fluoro-5-methoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide, N, .dbd.-dichloro-S-methylpheny-O- Z-chloro-δ-methoxy-1-triazolofi-6-c-pyrimidine-sulfonamide, N- (2-chloro-6-methoxycarbonyl) -5,7-dimethyl-1,2,4-triazolo [1 , 5-c] pyrimidine-2-sulfonamide (EP-A 0 343 752, US-A 4,988,812);
H) Benzoylcyclohexandione, z.B.H) benzoylcyclohexanediones, e.g.
2-(2-Chlor-4-methylsulfonylbenzoyl)-cyclohexan-1 ,3-dion (SC-0051 , EP-A 0 137 963), 2-(2-Nitrobenzoyl)-4,4-dimethyl-cyclohexan-1 ,3-dion (EP-A 0 274 634), 2-(2-Nitro-3-methylsulfonylbenzoyl)-4,4-dimethylcyclohexan-1 ,3-dion (WO 91/13548);2- (2-chloro-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione (SC-0051, EP-A-0 137 963), 2- (2-nitrobenzoyl) -4,4-dimethyl-cyclohexane-1, 3-dione (EP-A 0 274 634), 2- (2-nitro-3-methylsulfonylbenzoyl) -4,4-dimethylcyclohexane-1,3-dione (WO 91/13548);
I) Pyrimidinyloxy-pyridincarbonsäure- bzw. Pyrimidinyloxybenzoesäure- Derivate, z.B.I) pyrimidinyloxypyridinecarboxylic acid or pyrimidinyloxybenzoic acid derivatives, e.g.
3-(4,6-Dimethoxypyrimidin-2-yl)-oxy-pyridin-2-carbonsäurebenzylester (EP-A 0 249Benzyl 3- (4,6-dimethoxypyrimidin-2-yl) oxy-pyridine-2-carboxylate (EP-A 0 249
707),707)
3-(4,6-Dimethoxypyrimidin-2-yl)-oxy-pyridin-2-carbonsäuremethylester (EP-A 0 249Methyl 3- (4,6-dimethoxypyrimidin-2-yl) oxy-pyridine-2-carboxylate (EP-A 0 249
707), 2,6-Bis[(4,6-dimethoxypyrimidin-2-yl)-oxy]-benzoesäure (EP-A 0 321 846),707), 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) oxy] benzoic acid (EP-A 0 321 846),
2,6-Bis[(4,6-dimethoxypyrimidin-2-yl)-oxy]-benzoesäure-1-(ethoxycarbonyl-oxyethyl)- ester (EP-A 0 472 113);2,6-Bis [(4,6-dimethoxypyrimidin-2-yl) oxy] benzoic acid 1- (ethoxycarbonyl oxyethyl) ester (EP-A 0 472 113);
J) S-(N-Aryl-N-alkyl-carbamoylmethyl)-dithiophosphonsäureester, wie S-[N-(4- Chlθφhenyl)-N-isopropyl-carbamoylmethyl]-O,O-dimethyl-dithiophosphat (Anilophos). K) Alkylazine, z.B. wie beschrieben 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 sowie auch DE-A-19828519, WO-A-98/34925, WO-A-98/42684, WO-A-99/18100, WO-A-99/19309, WO-A-99/37627 und WO-A-99/65882, vorzugsweise solche der Formel (K)J) S- (N-aryl-N-alkyl-carbamoylmethyl) -dithiophosphonic acid esters, such as S- [N- (4-chloro-phenyl) -N-isopropyl-carbamoyl-methyl] -O, O-dimethyl-dithiophosphate (anilophos). K) Alkylazines, for example 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 (K)
H wonn R1 (CrC4)-Alkyl oder (CrC4)-Haloalkyl; R2 (d-C^-Alkyl, (C3-C6)-Cycloalkyl oder (C3-C6)-Cycloalkyl-(CrC4)-Alkyl und A -CH2-, -CH2-CH2-, -CH2-CH2-CH2-, -O-, -CH2-CH2-O-, -CH2-CH2-CH2-O- bedeuten, besonders bevorzugt solche der Formel K1-K7H is R 1 (C r C 4 ) alkyl or (C r C 4 ) haloalkyl; R 2 is (C 1 -C 4 ) alkyl, (C 3 -C 6 ) -cycloalkyl or (C 3 -C 6 ) -cycloalkyl (C 1 -C 4 ) -alkyl and A is -CH 2 -, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, -O-, -CH 2 -CH 2 -O-, -CH 2 -CH 2 -CH 2 -O- mean, particularly preferably those of the formula K1-K7
(K6) (K6)
L) phosphorhaltige Herbizide, z.B. eine oder mehrere Verbindungen der Formel (IV) oder deren Derivate wie Salze,L) phosphorus-containing herbicides, e.g. one or more compounds of the formula (IV) or derivatives thereof, such as salts,
worin wherein
Z1 einen Rest der Formel -OM, -NHCH(CH3)CONHCH(CH3)CO2M oder -NHCH(CH3)CONHCH[CH2CH(CH3)2]CO2M und M = H oder ein Salz bildendes Kation bedeuten, und/oder eine oder mehrere Verbindungen der Formel (V) oder deren Derivate wie Salze,Z 1 is a radical of the formula -OM, -NHCH (CH 3 ) CONHCH (CH 3 ) CO 2 M or -NHCH (CH 3 ) CONHCH [CH 2 CH (CH 3 ) 2] CO 2 M and M = H or a salt-forming cation , and / or one or more compounds of the formula (V) or derivatives thereof, such as salts,
(V) worin(V) wherein
Z2 einen Rest der Formel CN oder CO2R1 bedeutet, in dem R1 = Q oder ein Salz bildendes Kation ist und dabei Q = H, Alkyl, Alkenyl, Alkoxyalkyl oder C6-Cio-Aryl, das unsubstituiert oder substituiert ist und vorzugsweise unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Alkyl, Alkoxy, Halogen, CF3, NO2 und CN substituiert ist, und R2,R3 jeweils unabhängig voneinander H, Alkyl, Cβ-Cio-Aryl, das unsubstituiert oder substituiert ist und vorzugsweise unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Alkyl, Alkoxy, Halogen, CFß, NO2 und CN substituiert ist, oder Biphenyl oder ein Salz bildendes Kation bedeuten.Z 2 is a radical of the formula CN or CO 2 R 1 in which R 1 is Q or a salt-forming cation and Q = H, alkyl, alkenyl, alkoxyalkyl or C 6 -C 10 -aryl, which is unsubstituted or substituted and preferably unsubstituted or substituted by one or more radicals from the group alkyl, alkoxy, halogen, CF 3 , NO 2 and CN, and R 2 , R 3 are each independently H, alkyl, Cβ-Cio-aryl, which is unsubstituted or substituted and is preferably unsubstituted or substituted by one or more radicals from the group alkyl, alkoxy, halogen, CF ß , NO 2 and CN , or biphenyl or a salt-forming cation.
Beispiele für Wirkstoffe der Formel (IV) und (V) sind folgende:Examples of active compounds of the formula (IV) and (V) are the following:
- Glufosinate und dessen Ammoniumsalz in racemischer Form, d.h. 2-Amino-4-Glufosinate and its ammonium salt in racemic form, i. 2-Amino-4-
[hydroxy(methyl)phosphinoyl]-butansäure bzw. dessen Ammoniumsalz,[hydroxy (methyl) phosphinoyl] -butanoic acid or its ammonium salt,
- das L-Enantiomer von Glufosinate und dessen Ammoniumsalz, - Bilanafos/Bialaphos, d.h. L-2-Amino-4-[hydroxy(methyl)phosphinoyl]-butanoyl-L- alaninyl-L-alanin und dessen Natriumsalz- the L-enantiomer of glufosinate and its ammonium salt, - bilanafos / bialaphos, i. L-2-amino-4- [hydroxy (methyl) phosphinoyl] butanoyl-L-alaninyl-L-alanine and its sodium salt
- Glyphosate.- glyphosate.
M) Carbamate, z.B. Asulam, Carbetamide, Chloropham und Propham;M) carbamates, e.g. Asulam, Carbetamide, Chloropham and Propham;
N) Benzofurane, z.B. Benfuresate und Ethofumesate;N) benzofurans, e.g. Benfuresate and Ethofumesate;
O) Phytohormone;O) phytohormones;
P) Auxine und Auxinanaloga, z.B. 4-lndol-3-buttersäure, lndol-3-essigsäure, 1- Naphthylessigsäure, 2-(1-Naphthyl)acetamid und 2-Naphthyloxyessigsäure;P) Auxins and auxin analogs, e.g. 4-indole-3-butyric acid, indole-3-acetic acid, 1-naphthylacetic acid, 2- (1-naphthyl) acetamide and 2-naphthyloxyacetic acid;
Q) Zytokinine, z.B. Cythokinin, Kinetin und 6-Benzylaminopurin;Q) cytokinins, e.g. Cythokinin, Kinetin and 6-Benzylaminopurine;
R) Gibberelline, z.B. Gibberillinsäure, Gibberillin A4 und A7;R) gibberellins, e.g. Gibberillic Acid, Gibberillin A4 and A7;
S) Absissinsäure- und deren Derivate;S) absissinic acid and its derivatives;
T) Ethylenvoriäufer, z.B. Ethephon;T) ethylene precursors, e.g. ethephon;
U) Herbizide aus der Gruppe der Fettsäuresynthetase-Inhibitoren; V) Harnstoffe, z.B. Chlorotoluron, Dimefuron, Diuron, Fluometuron, Isoproturon, Isouron, Karbutilate, Linuron, Methabenzthiazuron, Metobenzuron, Metoxuron, Monolinuron, Neburon, Siduron und Tebuthiuron undU) herbicides from the group of fatty acid synthetase inhibitors; Ureas, eg chlorotoluron, dimefuron, diuron, fluometuron, isoproturon, isourone, carbutilates, linuron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron and tebuthiuron and
W) Metamitron.W) Metamitron.
X) Hydroxybenzonitrile, z.B. wie Bromoxynil und loxynil und deren Salze und Ester, wie Bromoxyniloctanoat und loxyniloctanoat.X) hydroxybenzonitriles, e.g. such as bromoxynil and loxynil and their salts and esters such as bromoxyniloctanoate and loxyniloctanoate.
Die agrochemischen Wirkstoffe können auch Wachstumsregulatoren sein. Beispiele hierfür sind Ethephon, Tribufos, Cyclanilide und Thidiazuron.The agrochemical active substances can also be growth regulators. Examples of these are ethephon, tribufos, cyclanilides and thidiazuron.
Die Herbizide (Pflanzenwuchsregulatoren) der Gruppen A bis X sind beispielsweise aus den oben jeweils genannten Schriften und/oder aus "The Pesticide Manual", 12. Auflage (2000) bis 14. Auflage (2006), The British Crop Protection Council, "Agricultural Chemicals Book Il - Herbicides -", by WT. Thompson, Thompson Publications, Fresno CA, USA 1990 und "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990, bekannt.The herbicides (plant growth regulators) of groups A to X, for example, from the above-mentioned writings and / or from "The Pesticide Manual", 12th edition (2000) to 14th edition (2006), 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.
Safenersafener
Beispiele für Safener sind unter anderem:Examples of safeners include:
a) Verbindungen der Formeln (S-Il) bis (S-IV),a) compounds of the formulas (S-II) to (S-IV),
(S-Il) (S-III) (S-IV) wobei die Symbole und Indizes folgende Bedeutungen haben: n' ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; T ist eine (Ci oder C2)-Alkandiylkette, die unsubstituiert oder mit einem oder zwei (CrC4)Alkylresten oder mit [(CrC3)-Alkoxy]-carbonyl substituiert ist;(S-II) (S-III) (S-IV) where the symbols and indices have the following meanings: n 'is a natural number from 0 to 5, preferably 0 to 3; T is a (Ci or C2) -alkanediyl chain which is [alkoxy (C 3 r C)] is carbonyl unsubstituted or substituted with one or two (CrC 4) alkyl or;
W ist ein unsubstituierter oder substituierter divalenter heterocyclischer Rest aus der Gruppe der teilungesättigten oder aromatischen Fünfring-Heterocyclen mit 1 bis 3 Heteroringatomen des Typs N oder O, wobei mindestens ein N-Atom und höchstens ein O-Atom im Ring enthalten ist, vorzugsweise ein Rest aus der Gruppe (W1) bis (W4),W is an unsubstituted or substituted divalent heterocyclic radical from the group of unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring N or O atoms, at least one N atom and at most one O atom in the ring, preferably a radical from the group (W1) to (W4),
m' ist 0 oder 1 ;m 'is 0 or 1;
R17, R19 sind gleich oder verschieden Halogen, (CrC4)Alkyl, (C1-C4)AIkOXy, Nitro oder (CrC4)Haloalkyl;R 17 , R 19 are identical or different halogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, nitro or (C r C 4 ) haloalkyl;
R18, R20 sind gleich oder verschieden OR24, SR24 oder NR24R25 oder ein gesättigter oder ungesättigter 3- bis 7-gliedriger Heterocyclus mit mindestens einem N-Atom und bis zu 3 Heteroatomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (S-Il) bzw. (S-III) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (CrC4)Alkyl,R 18 , R 20 are identical or different OR 24 , SR 24 or NR 24 R 25 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S. which is connected via the N atom to the carbonyl group in (S-II) or (S-III) and unsubstituted or by radicals from the group (C 1 -C 4 ) alkyl,
(CrC4)Alkoxy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel OR24, NHR25 oder N(CH3)2, insbesondere der Formel OR24;(C r C 4 ) alkoxy or optionally substituted phenyl, preferably a radical of the formula OR 24 , NHR 25 or N (CH 3 ) 2 , in particular of the formula OR 24 ;
R24 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen;R 24 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms;
R25 ist Wasserstoff, (CrC6)Alkyl, (CrC6)Alkoxy oder substituiertes oder unsubstituiertes Phenyl;R 25 is hydrogen, (CrC 6) alkyl, (C r C6) alkoxy, or substituted or unsubstituted phenyl;
Rx ist H, (CrCβ)Alkyl, CrC8(Haloalkyl), (Ci-C4)Alkoxy(C1-C8)Alkyl, Cyano oder COOR26, worin R26 Wasserstoff, (CrC8)Alkyl, (CrC8)Haloalkyl, (CrC4)Alkoxy- (Ci-C4)alkyl, (CrCeJHydroxyalkyl, (C3-Ci2)Cycloalkyl oder Tri-(Ci-C4)-alkyl- silyl ist;R x is H, (C r Cβ) alkyl, C r C 8 (haloalkyl), (Ci-C 4 ) alkoxy (C 1 -C 8 ) alkyl, cyano or COOR 26 , wherein R 26 is hydrogen, (C r C 8 ) alkyl, (C r C 8 ) haloalkyl, (C r C 4 ) alkoxy (Ci-C 4) alkyl, (CrCeJHydroxyalkyl, (C3-Ci2) -cycloalkyl or tri- (Ci-C4) alkyl silyl;
R27, R28, R29 sind gleich oder verschieden Wasserstoff, (CrC8)Alkyl,R 27 , R 28 , R 29 are identical or different hydrogen, (C 1 -C 8 ) alkyl,
(CrCβJHaloalkyl, (C3-Ci2)Cycloalkyl oder substituiertes oder unsubstituiertes Phenyl;(CrCβJHaloalkyl, (C3-Ci2) cycloalkyl or substituted or unsubstituted phenyl;
R21 ist (CrC4)Alkyl, (CrC4)Haloalkyl, (C2-C4)Alkenyl, (C2-C4)Haloalkenyl, (C3-C7)Cycloalkyl, vorzugsweise Dichlormethyl;R 21 is (CrC 4) alkyl, (C r C4) haloalkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) haloalkenyl, (C 3 -C 7) cycloalkyl, preferably dichloromethyl;
R22, R23 ist gleich oder verschieden Wasserstoff, (CrC4)Alkyl, (C2-C4)Alkenyl,R 22 , R 23 is identical or different hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl,
(C2-C4)Alkinyl, (CrC4)Haloalkyl, (C2-C4)Haloalkenyl, (CrC4)Alkylcarbamoyl- (CrC4)alkyl, (C2-C4)Alkenylcarbamoyl-(CrC4)alkyl, (Ci-C4)Alkoxy-(d-(C 2 -C 4 ) alkynyl, (C r C 4 ) haloalkyl, (C 2 -C 4 ) haloalkenyl, (C r C 4 ) alkylcarbamoyl (C r C 4 ) alkyl, (C 2 -C 4 ) alkenylcarbamoyl (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy (d-
C4)alkyl, Dioxolanyl-(CrC4)alkyl, Thiazolyl, Furyl, Furylalkyl, Thienyl, Piperidyl, substituiertes oder unsubstituiertes Phenyl, oder R22 und R23 bilden zusammen einen substituierten oder unsubstituierten heterocyclischen Ring, vorzugsweise einen Oxazolidin-, Thiazolidin-, Piperidin-, Morpholin-, Hexahydropyrimidin- oder Benzoxazinring; vorzugsweise Safener folgender Untergruppen von Verbindungen der Formeln (S-Il) bis (S-IV):C 4 ) alkyl, dioxolanyl- (C 1 -C 4 ) alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R 22 and R 23 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine , Piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably safeners of the following subgroups of compounds of the formulas (S-II) to (S-IV):
- Verbindungen vom Typ der Dichlorphenylpyrazolin-3-carbonsäure (d.h. der Formel (S-Il), worin W = (W1) und (R17V = 2,4-Cl2), vorzugsweise Verbindungen wie 1 -(2,4-Dichloφhenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazolin-3- carbonsäureethylester (ll-1 , Mefenpyr-diethyl), Mefenpyr-dimethyl und Mefenpyr (H-O), und verwandte Verbindungen, wie sie in der WO-A-91 /07874 beschrieben sind;Compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (ie of the formula (S-II) in which W = (W1) and (R 17 V = 2,4-Cl 2 ), preferably compounds such as 1- (2,4-Cl 2 ) Dichloro-phenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (II-1, mefenpyr-diethyl), mefenpyr-dimethyl and mefenpyr (HO), and related compounds as described in WO-A -91 / 07874 are described;
- Derivate der Dichlorphenylpyrazolcarbonsäure (d.h. der Formel (S-II), worin W = (W2) und (R17V = 2,4-Cl2 ist ), vorzugsweise Verbindungen wie 1-(2,4-Derivatives of the dichlorophenylpyrazolecarboxylic acid (ie of the formula (S-II) in which W = (W 2 ) and (R 17 V = 2,4-Cl 2 ), preferably compounds such as 1- (2,4-Cl 2 )
Dichlorphenyl)-5-methyl-pyrazol-3-carbonsäureethylester (II-2), 1 -(2,4- Dichloφhenyl)-5-isopropyl-pyrazol-3-carbonsäureethylester (II-3), 1 -(2,4- Dichloφhenyl)-5-(1 ,1-dimethyl-ethyl)pyrazol-3-carbonsäureethylester (ll-4), 1 -(2,4-Dichloφhenyl)-5-phenyl-pyrazol-3-carbonsäureethylester (II-5) und verwandte Verbindungen, wie sie in EP-A-0333131 und EP-A-0269806 beschrieben sind; - Verbindungen vom Typ der Triazolcarbonsäuren (d.h. der Formel (S-Il), worin W = (W3) und (R17V = 2,4-Cb ist), vorzugsweise Verbindungen wie Fenchlorazol- ethyl, d.h. 1-(2,4-Dichlorphenyl)-5-trichlormethyl-(1 H)-1 ,2,4-triazol-3- carbonsäureethylester (II-6), und verwandte Verbindungen (siehe EP-A-0174562 und EP-A-0346620);Dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (II-2), 1 - (2,4-dichloro-phenyl) -5-isopropyl-pyrazole-3-carboxylic acid ethyl ester (II-3), 1 - (2,4- Dichloφhenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (II-4), 1 - (2,4-Dichloo-phenyl) -5-phenyl-pyrazole-3-carboxylic acid ethyl ester (II-5) and related compounds as described in EP-A-0333131 and EP-A-0269806; Compounds of the type of the triazolecarboxylic acids (ie of the formula (S-II) in which W = (W3) and (R 17 V = 2,4-Cb), preferably compounds such as fenchlorazolethyl, ie 1- (2,4 -Dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (II-6), and related compounds (see EP-A-0174562 and EP-A-0346620);
- Verbindungen vom Typ der 5-Benzyl- oder 5-Phenyl-2-isoxazolin-3-carbonsäure oder der 5,5-Diphenyl-2-isoxazolin-3-carbonsäure wie Isoxadifen (11-12), (worin W = (W4) ist), vorzugsweise Verbindungen wie 5-(2,4-Dichlorbenzyl)-2-isoxazolin-3- carbonsäureethylester (II-7) oder 5-Phenyl-2-isoxazolin-3-carbonsäureethylester (Ii-S) und verwandte Verbindungen, wie sie in WO-A- 91/08202 beschrieben sind, oder der 5,5-Diphenyl-2-isoxazolin-carbonsäureethylester (II-9, Isoxadifen-ethyl) oder -n-propylester (11-10) oder der 5-(4-Fluorphenyl)-5-phenyl-2-isoxazolin-3- carbonsäureethylester (11-11 ), wie sie in der WO-A-95/07897 beschrieben sind.Compounds of the 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid type or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, such as isoxadifen (11-12), (wherein W = (W4 ), preferably compounds such as ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (II-7) or 5-phenyl-2-isoxazoline-3-carboxylate (II-S) and related compounds, as described in WO-A-91/08202, or the ethyl 5,5-diphenyl-2-isoxazoline-carboxylate (II-9, isoxadifen-ethyl) or n-propyl ester (11-10) or the 5- (5-10) 4-fluorophenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (11-11), as described in WO-A-95/07897.
- Verbindungen vom Typ der 8-Chinolinoxyessigsäure, z.B. solche der Formel (S- III), worin (R19V = 5-CI, R20 = OR24 und T = CH2 ist, vorzugsweise die- Compounds of the type of 8-quinolinoxyacetic acid, for example those of the formula (S-III), wherein (R 19 V = 5-CI, R 20 = OR 24 and T = CH 2 , preferably the
Verbindungen (5-Chlor-8-chinolinoxy)essigsäure-(1-methylhexyl)-ester (111-1 , Cloquintocet-mexyl), (5-Chlor-8-chinolinoxy)essigsäure-(1 ,3-dimethyl-but-1 -yl)- ester (III-2), (5-Chlor-8-chinolinoxy)essigsäure-4-allyl-oxy-butylester (III-3), (5- Chlor-8-chinolinoxy)essigsäure-1-allyloxy-prop-2-ylester (lll-4), (5-Chlor-8- chinolinoxy)essigsäureethylester (III-5), (5-Chlor-8- chinolinoxy)essigsäuremethylester (III-6), (5-Chlor-8- chinolinoxy)essigsäureallylester (lll-7), (5-Chlor-8-chinolinoxy)essigsäure-2-(2- propyliden-iminoxy)-1-ethylester (III-8), (5-Chlor-8-chinolinoxy)essigsäure-2-oxo- prop-1-ylester (III-9), (5-Chlor-8-chinolinoxy)essigsäure (111-10) und dessen Salze wie sie z.B. in der WO-A-02/34048 beschrieben sind, und verwandteCompounds (5-chloro-8-quinolinoxy) acetic acid (1-methylhexyl) ester (111-1, cloquintocet-mexyl), (5-chloro-8-quinolinoxy) acetic acid (1, 3-dimethyl-but-1 -yl) ester (III-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyl oxy-butyl ester (III-3), (5-chloro-8-quinolinoxy) acetic acid 1-allyloxy prop-2-yl-ester (III-4), (5-chloro-8-quinolinoxy) acetic acid ethyl ester (III-5), (5-chloro-8-quinolinoxy) acetic acid methyl ester (III-6), (5-chloro-8- quinolinoxy) allyl acetate (III-7), (5-chloro-8-quinolinoxy) acetic acid 2- (2-propylidene-iminoxy) -1-ethyl ester (III-8), (5-chloro-8-quinolinoxy) acetic acid 2-oxo-prop-1-yl-ester (III-9), (5-chloro-8-quinolinoxy) acetic acid (III-10) and its salts as described, for example in WO-A-02/34048 and related
Verbindungen, wie sie in EP-A-0860750, EP-A-0094349 und EP-A-0191736 oder EP-A-0492366 beschrieben sind.Compounds as described in EP-A-0860750, EP-A-0094349 and EP-A-0191736 or EP-A-0492366.
- Verbindungen vom Typ der (5-Chlor-8-chinolinoxy)-malonsäure, d.h. der Formel (S-III), worin (R19V = 5-CI, R20= OR24, T = -CH(COO-Alkyl)- ist, vorzugsweise die Verbindungen (5-Chlor-8-chinolinoxy)-malonsäure-diethylester (111-11 ), (5-Chlor-Compounds of the (5-chloro-8-quinolinoxy) -malonic acid type, ie of the formula (S-III), wherein (R 19 V = 5-Cl, R 20 = OR 24 , T = -CH (COO-alkyl ) -, preferably the compounds (5-chloro-8-quinolinoxy) -malonic acid diethyl ester (111-11), (5-chloro
8-chinolinoxy)-malonsäurediallylester, (5-Chlor-8-chinolinoxy)-malonsäure- methyl-ethylester und verwandte Verbindungen, wie sie in EP-A-0582198 beschrieben sind. - Verbindungen vom Typ der Dichloracetamide, d.h. der Formel (S-IV), vorzugsweise: N,N-Diallyl-2,2-dichloracetamid (Dichlormid (IV-1 ), aus US 4,137,070), 4-Dichloracetyl-3,4-dihydro-3-methyl-2H-1 ,4-benzoxazin (IV-2,8-quinolinoxy) -malonic acid diallyl ester, (5-chloro-8-quinolinoxy) -malonic acid methyl ethyl ester and related compounds as described in EP-A-0582198. Compounds of the dichloroacetamide type, ie of the formula (S-IV), preferably: N, N-diallyl-2,2-dichloroacetamide (dichloromide (IV-1), from US 4,137,070), 4-dichloroacetyl-3,4- dihydro-3-methyl-2H-1,4-benzoxazine (IV-2,
Benoxacor, aus EP 0149974), N1 ,N2-Diallyl-N2-dichloracetylgIycinamid (DKA-24 (IV-3), aus HU 2143821), 4-Dichloracetyl-1-oxa-4-aza-spiro[4,5]decan (AD-67), 2,2-Dichlor-N-(1 ,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamid (PPG-1292), 3- Dichloracetyl-2,2,5-trimethyloxazolidin (R-29148, IV-4), 3-Dichloracetyl-2,2- dimethyl-5-phenyloxazolidin, 3-Dichloracetyl-2,2-dimethyl-5-(2-thienyl)oxazolidin,Benoxacor, from EP 0149974), N1, N2-diallyl-N2-dichloroacetylglycine amide (DKA-24 (IV-3), from HU 2143821), 4-dichloroacetyl-1-oxa-4-aza-spiro [4,5] decane (AD-67), 2,2-dichloro-N- (1,3-dioxolan-2-ylmethyl) -N- (2-propenyl) acetamide (PPG-1292), 3-dichloroacetyl-2,2,5- trimethyloxazolidine (R-29148, IV-4), 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine, 3-dichloroacetyl-2,2-dimethyl-5- (2-thienyl) oxazolidine,
3-Dichloracetyl-5-(2-furanyl)-2,2-dimethyloxazolidin (Furilazole (IV-5), MON 13900), 1 -Dichloracetyl-hexahydro-3,3,8a-trimethylpyrrolo[1 ,2-a]pyrimidin-6(2H)- on (Dicyclonon, BAS 145138), b) eine oder mehreren Verbindungen aus Gruppe: 1 ,8-Naphthalsäureanhydrid, Methyl-diphenylmethoxyacetat, 1-(2-Chlorbenzyl)-3-(1- methyl-1-phenylethyl)harnstoff (Cumyluron), O,O-Diethyl S-2-ethylthioethyl phosphordithioat (Disulfoton), 4-Chlorphenyl-methylcarbamat (Mephenate), O1O- Diethyl-O-phenylphosphorotioat (Dietholate), 4-Carboxy-3,4-dihydro-2H-1 - benzopyran-4-essigsäure (CL-304415, CAS-Regno: 31541-57-8), Cyanomethoxyimino(phenyl)acetonitril (Cyometrinil), 1 ,3-Dioxolan-2- ylmethoxyimino(phenyl)acetonitril (Oxabetrinil), 41-Chlor-2,2,2-trifluoracetophenon-O- 1 ,3-dioxolan-2-ylmethyloxim (Fluxofenim), 4,6-Dichlor-2-phenylpyrimidin (Fenclorim), Benzyl-2-chlor-4-trifluormethyl-1 ,3-thiazol-5-carboxylat (Flurazole), 2-Dichlormethyl- 2-methyl-1 ,3-dioxolan (MG-191 ), N-(4-Methylphenyl)-N'-(1 -methyl-1 - phenylethyl)harnstoff (Dymron), (2,4-Dichlorphenoxy)essigsäure (2,4-D), (4-3-dichloroacetyl-5- (2-furanyl) -2,2-dimethyloxazolidine (furilazole (IV-5), MON 13900), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo [1,2-a] pyrimidine -6 (2H) -one (dicyclonone, BAS 145138), b) one or more compounds from the group: 1, 8-naphthalic anhydride, methyl-diphenylmethoxyacetate, 1- (2-chlorobenzyl) -3- (1-methyl-1-) phenylethyl) urea (cumyluron), O, O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton), 4-chlorophenyl-methylcarbamate (Mephenate), O 1 O- diethyl-O-phenylphosphorotioat (Dietholate), 4-carboxy-3, 4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, CAS Regno: 31541-57-8), cyanomethoxyimino (phenyl) acetonitrile (cyometrinil), 1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil), 4 1 -chloro-2,2,2-trifluoroacetophenone-O-1, 3-dioxolan-2-ylmethyloxime (Fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl-2- chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole), 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), N- (4-methylphenyl) -N '- ( 1 -methyl-1-phenylethyl) urea (dymron), (2,4-dichlorophenoxy) acetic acid (2,4-D), (4-
Chlorphenoxy)essigsäure, (R,S)-2-(4-Chlor-o-tolyloxy)propionsäure (Mecoprop), 4- (2,4-Dichlθφhenoxy)buttersäure (2,4-DB), (4-Chlor-o-tolyloxy)essigsäure (MCPA), 4- (4-Chlor-o-tolyloxy)buttersäure, 4-(4-Chlorphenoxy)buttersäure, 3,6-Dichlor-2- methoxybenzoesäure (Dicamba), 1 -(Ethoxycarbonyl)ethyl 3,6-dichlor-2- methoxybenzoat (Lactidichlor) sowie deren Salze und Ester, vorzugsweise (CrC8); c) N-Acylsulfonamide der Formel (S-V) und ihre Salze, Chlorophenoxy) acetic acid, (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB), (4-chloro-o -tolyloxy) acetic acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (Dicamba), 1- (ethoxycarbonyl) ethyl 3 , 6-dichloro-2-methoxybenzoate (lactidichloro) and their salts and esters, preferably (CrC 8 ); c) N-acylsulfonamides of the formula (SV) and their salts,
worinwherein
R30 Wasserstoff, einen Kohlenwasserstoffrest, einen Kohlenwasserstoffoxyrest, einen Kohlenwasserstoffthiorest oder einen Heterocyclylrest, der vorzugsweise über ein C-Atom gebunden ist, wobei jeder der letztgenannten 4 Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Formyl, Carbonamid, Sulfonamid und Reste der Formel -Za-Ra substituiert ist, wobei jeder Kohlenwasserstoffteil vorzugsweise 1 bis 20 C-Atome aufweist und ein C-haltiger Rest R30 inklusive Substituenten vorzugsweise 1 bis 30 C-Atome aufweist; R31 Wasserstoff oder (d-C-O-Alkyl, vorzugsweise Wasserstoff, oder R30 und R31 zusammen mit der Gruppe der Formel -CO-N- den Rest eines 3- bis 8-gliedrigen gesättigten oder ungesättigten Rings;R 30 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro , Amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula -Z a -R a is substituted, wherein each hydrocarbon moiety preferably 1 to 20 carbon atoms and a C-containing radical R 30 including substituents preferably 1 to 30 Having C atoms; R 31 is hydrogen or (dCO-alkyl, preferably hydrogen, or R 30 and R 31 together with the group of the formula -CO-N- the radical of a 3- to 8-membered saturated or unsaturated ring;
R32 gleich oder verschieden Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Formyl, CONH2, SO2NH2 oder einen Rest der Formel -Zb-Rb ;R 32 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH 2 , SO 2 NH 2 or a radical of the formula -Z b -R b ;
R33 Wasserstoff oder (d-C-O-Alkyl, vorzugsweise H; R34 gleich oder verschieden Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, CHO, CONH2, SO2NH2 oder einen Rest der Formel -Zc-Rc ;R 33 is hydrogen or (dCO-alkyl, preferably H; R 34 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH 2 , SO 2 NH 2 or a radical of the formula -Z c -R c ;
Ra einen Kohlenwasserstoffrest oder einen Heterocyclylrest, wobei jeder der beiden letztgenannten Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Mono- und Di-[(Ci-C4)-alkyl]-amino substituiert ist, oder einen Alkylrest, in dem mehrere, vorzugsweise 2 oder 3, nicht benachbarte CH2-Gruppen jeweils durch ein Sauerstoffatom ersetzt sind; Rb,Rc gleich oder verschieden einen Kohlenwasserstoffrest oder einenR a is a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [(Ci-C 4 ) - alkyl] -amino, or an alkyl radical in which several, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom; R b , R c, identically or differently, are a hydrocarbon radical or a
Heterocyclylrest, wobei jeder der beiden letztgenannten Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Phosphoryl, Halogen- (CrC-O-alkoxy, Mono- und Di-[(Ci-C4)-alkyl]-amino substituiert ist, oder einen Alkylrest, in dem mehrere, vorzugsweise 2 oder 3, nicht benachbarte CH2-Gruppen jeweils durch ein Sauerstoffatom ersetzt sind;Heterocyclyl radical, wherein each of the last two radicals unsubstituted or by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halogeno (C 1 -C 0 -alkoxy, mono- and di- [(C 1 -C 4 ) -alkyl] -amino is substituted, or an alkyl radical in which a plurality, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom;
Za eine divalente Gruppe der Formel -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-,Z a is a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-,
-O-CO-, -S-CO-, -SO-, -SO2-, -NR*-, -CO-NR*-, -NR*-CO-, -SO2-NR*- oder -NR*-SO2-, wobei die rechts angegebene Bindung der jeweiligen divalenten Gruppe die Bindung zum Rest Ra ist und wobei die R* in den letztgenannten 5 Resten unabhängig voneinander jeweils H, (C-ι-C4)-Alkyl oder HaIo-(CrC4)- alkyl bedeuten;-O-CO-, -S-CO-, -SO-, -SO 2 -, -NR * -, -CO-NR * -, -NR * -CO-, -SO 2 -NR * - or -NR * -SO 2 -, where the bond of the respective divalent group indicated on the right is the bond to the radical R a and where the R * in the last-mentioned 5 radicals are each independently H, (C 1 -C 4 ) -alkyl or halo (C 1 -C 4 ) -alkyl;
Zb, Zc unabhängig voneinander eine direkte Bindung oder eine divalente Gruppe der Formel -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO2-, -NR*-, -SO2-NR*-, -NR*-SO2-, -CO-NR*- oder -NR*-CO-, wobei die rechts angegebene Bindung der jeweiligen divalenten Gruppe die Bindung zum Rest Rb bzw. Rc ist und wobei die R* in den letztgenannten 5 Resten unabhängig voneinander jeweils H, (Ci-C4)-Alkyl oder Halo-(CrC4)-alkyl bedeuten; n eine ganze Zahl von O bis 4, vorzugsweise 0, 1 oder 2, insbesondere O oder 1 , und m eine ganze Zahl von O bis 5, vorzugsweise 0, 1 , 2 oder 3, insbesondere 0, 1 oder 2; bedeuten; vorzugsweise Safener von Verbindungen der Formel (S-V), worinZ b , Z c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO 2 -, -NR * -, -SO 2 -NR * -, -NR * -SO 2 -, -CO-NR * - or -NR * -CO-, where the bond of the respective divalent group indicated on the right is the bond to the radical R b or R c and where the R * in the last-mentioned 5 radicals are each independently H, (Ci-C4) -alkyl or halo- (CrC 4 ) - alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular O or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; mean; preferably safeners of compounds of formula (SV) wherein
- R30 = H3C-O-CH2-, R31 = R33 = H, R34 = 2-OMe ist (V-1 ), - R30 = H3C-O-CH2-, R31 = R33 = H, R34 = 2-OMe-5-CI ist (V-2),R 30 = H 3 CO-CH 2 -, R 31 = R 33 = H, R 34 = 2-OMe is (V-1), - R 30 = H 3 CO-CH 2 -, R 31 = R 33 = H, R 34 = 2-OMe-5-CI is (V-2),
- R30 = Cyclopropyl, R31 = R33 = H, R34 = 2-OMe ist (V-3),R 30 = cyclopropyl, R 31 = R 33 = H, R 34 = 2-OMe is (V-3),
- R30 = Cyclopropyl, R31 = R33 = H, R34 = 2-OMe-5-CI ist (V-4),R 30 = cyclopropyl, R 31 = R 33 = H, R 34 = 2-OMe-5-CI is (V-4),
- R30 = Cyclopropyl, R31 = R33 = H, R34 = 2-Me ist (V-5),R 30 = cyclopropyl, R 31 = R 33 = H, R 34 = 2-Me is (V-5),
- R30 = tert. Butyl, R31 = R33 = H, R34 = 2-OMe ist (V-6).R 30 = tert. Butyl, R31 = R33 = H, R34 = 2-OMe is (V-6).
d) Acylsulfamoylbenzoesäureamide der allgemeinen Formel (S-Vl), gegebenenfalls auch in Salzform, worind) Acylsulfamoylbenzoesäureamide of the general formula (S-Vl), optionally in salt form, wherein
X3 CH oder N;X 3 is CH or N;
R35 Wasserstoff, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die beiden letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, CHO, CONH2, SO2NH2 und Za-Ra substituiert sind;R 35 is hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 and Z a -R are a substituted;
R36 Wasserstoff, Hydroxy, (CrC6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C1-C6)-R 36 is hydrogen, hydroxy, (CrC 6) alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkynyl, (C 1 -C 6) -
Alkoxy, (C2-C6)-Alkenyloxy, wobei die fünf letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Hydroxy, (Ci-C-O-Alkyl, (C1-C4J-AIkOXy und (C1-C4)- Alkylthio substituiert sind, oderAlkoxy, (C 2 -C 6 ) alkenyloxy, wherein the last five radicals mentioned optionally substituted by one or more identical or different radicals selected from the group consisting of halogen, hydroxy, (Ci-CO-alkyl, (C 1 -C 4 J-AIkOXy and (C 1 -C 4 ) -alkylthio, or
R35 und R36 zusammen mit dem sie tragenden Stickstoffatom einen 3- bis 8- gliedrigen gesättigten oder ungesättigten Ring; R37 Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, CHO, CONH2, SO2NH2 oder Zb-Rb;R 35 and R 36 together with the nitrogen atom carrying them have a 3- to 8-membered saturated or unsaturated ring; R 37 is halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 or Z b -R b ;
R38 Wasserstoff, (Ci-C4)-Alkyl, (C2-C4)-Alkenyl oder (C2-C4)-Alkinyl;R 38 is hydrogen, (C 1 -C 4 ) -alkyl, (C 2 -C 4 ) -alkenyl or (C 2 -C 4 ) -alkynyl;
R39 Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Phosphoryl, CHO, CONH2,R 39 is halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH 2 ,
SO2NH2 oder Zc-Rc; Ra einen (C2-C2o)-Alkylrest, dessen Kohlenstoffkette ein- oder mehrfach durch Sauerstoffatome unterbrochen ist, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die zwei letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Mono- und Di-[(CrC4)-alkyl]-amino substituiert sind;SO 2 NH 2 or Z c -R c ; R a is a (C 2 -C 2 o) -alkyl radical whose carbon chain is mono- or interrupted by oxygen atoms, is heterocyclyl or a hydrocarbon radical, where the last two radicals are optionally substituted by one or more identical or different radicals from the group halogen substituted [(C r C 4) -alkyl] amino - cyano, nitro, amino, hydroxyl, mono- and di;
Rb, Rc gleich oder verschieden einen (C2-C20)-Alkylrest, dessen Kohlenstoffkette ein- oder mehrfach durch Sauerstoffatome unterbrochen ist, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die zwei letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Phosphoryl, (C1-C4)-R b , R c, identically or differently, denote a (C 2 -C 20 ) -alkyl radical whose carbon chain is interrupted one or more times by oxygen atoms, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C 1 -C 4 ) -
Haloalkoxy, Mono- und Di-[(Ci-C4)-alkyl]-amino substituiert sind; Za eine divalente Einheit aus der Gruppe O, S1 CO1 CS1 C(O)O, C(O)S, SO, SO2,Haloalkoxy, mono- and di - [(Ci-C4) alkyl] amino substituted; Z a is a divalent unit from the group O, S 1 CO 1 CS 1 C (O) O, C (O) S, SO, SO 2 ,
NRd, C(O)NRd oder SO2NRd; Zb, Zc gleich oder verschieden eine direkte Bindung oder eine divalente Einheit aus der Gruppe O, S, CO, CS, C(O)O, C(O)S, SO, SO2, NRd, SO2NRd oderNR d , C (O) NR d or SO 2 NR d ; Z b , Z c, identically or differently, denote a direct bond or a divalent unit from the group O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , SO 2 NR d or
C(O)NRd;C (O) NR d ;
Rd Wasserstoff, (CrC4)-Alkyl oder (Ci-C4)-Haloalkyl; n eine ganze Zahl von O bis 4, und m für den Fall, dass X für CH steht, eine ganze Zahl von O bis 5, und für denR d is hydrogen, (C r C 4 ) -alkyl or (Ci-C 4 ) -haloalkyl; n is an integer from 0 to 4, and m in the case that X is CH, an integer from 0 to 5, and for the
Fall, dass X für N steht, eine ganze Zahl von O bis 4 bedeuten; vorzugsweise Safener von Verbindungen der Formel (S-Vl), in der X3 CH;Case that X is N, an integer from 0 to 4; preferably safeners of compounds of the formula (S-VI) in which X 3 CH;
R35 Wasserstoff, (CrC6)-Alkyl, (C3-C6)-Cycloalkyl, (C2-C6)-Alkenyl, (C5-C6)- Cycloalkenyl, Phenyl oder 3- bis 6-gliedriges Heterocyclyl mit bis zu dreiR 35 is hydrogen, (C 1 -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (C 2 -C 6 ) -alkenyl, (C 5 -C 6 ) -cycloalkenyl, phenyl or 3 to 6-membered heterocyclyl with up to three
Heteroatomen aus der Gruppe Stickstoff, Sauerstoff und Schwefel, wobei die sechs letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Substituenten aus der Gruppe Halogen, (CrC6)-Heteroatoms from the group consisting of nitrogen, oxygen and sulfur, where the six last-mentioned radicals are optionally substituted by one or more, identical or different substituents from the group halogen, (CrC 6 ) -
Alkoxy, (CrC6)-Haloalkoxy, (d-C2)-Alkylsulfinyl, (CrC2)-Alkylsulfonyl, (C3-C6)-Cycloalkyl, (C1-C4)-Alkoxycarbonyl, (CrC4)-Alkylcarbonyl und Phenyl und im Falle cyclischer Reste auch (CrC4)-Alkyl und (CrC4)-Haloalkyl substituiert sind; R36 Wasserstoff, (C-i-CβJ-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, wobei die drei letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Substituenten aus der Gruppe Halogen, Hydroxy, (C1-C4)-Alkoxy, (C r C 6) -haloalkoxy, (dC 2) alkylsulfinyl, (C r C 2) alkylsulfonyl, (C 3 -C 6) -cycloalkyl, (C 1 -C 4) alkoxycarbonyl, (C r C 4 ) -alkylcarbonyl and phenyl and in the case of cyclic radicals also (C 1 -C 4 ) -alkyl and (C 1 -C 4 ) -haloalkyl; R 36 is hydrogen, (C 1 -C 6 -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, where the last three radicals mentioned are optionally substituted by one or more, identical or different substituents from the group consisting of halogen , Hydroxy, (C 1 -C 4 ) -
Alkyl, (CrC4)-Alkoxy und (d-C4)-Alkylthio substituiert sind; R37 Halogen, (Ci-C4)-Haloalkyl, (Ci-C4)-Haloalkoxy, Nitro, (CrC4)-Alkyl, (C1-C4)-Alkyl, (C 1 -C 4 ) alkoxy and (C 1 -C 4 ) alkylthio; R 37 is halogen, (Ci-C 4) -haloalkyl, (Ci-C 4) -haloalkoxy, nitro, (CrC 4) alkyl, (C 1 -C 4) -
Alkoxy, (Ci-C4)-Alkylsulfonyl, (CrC4)-Alkoxycarbonyl oder (C1-C4)-Alkoxy, (Ci-C 4) alkylsulfonyl, (C r C4) -alkoxycarbonyl or (C 1 -C 4) -
Alkylcarbonyl; R38 Wasserstoff;alkylcarbonyl; R 38 is hydrogen;
R39 Halogen, Nitro, (CrC4)-Alkyl, (C1-C4)-Haloalkyl, (Ci-C4)-Haloalkoxy, (C3-C6)-R 39 is halogen, nitro, (C r C4) alkyl, (C 1 -C 4) -haloalkyl, (Ci-C 4) -haloalkoxy, (C 3 -C 6) -
Cycloalkyl, Phenyl, (d-C4)-Alkoxy, Cyano, (CrC4)-Alkylthio, (C1-C4)- Alkylsulfinyl, (CrC-O-Alkylsulfonyl, (CrC4)-Alkoxycarbonyl oder (Ci-C4)-Cycloalkyl, phenyl, (dC 4) alkoxy, cyano, (CrC 4) alkylthio, (C 1 -C 4) - Alkylsulfinyl, (CrC-O-alkylsulfonyl, (C r C4) -alkoxycarbonyl or (Ci-C 4) -
Alkylcarbonyl; n 0, 1 oder 2 und m 1 oder 2 bedeuten.alkylcarbonyl; n is 0, 1 or 2 and m is 1 or 2.
Insbesondere Verbindungen vom Typ der Acylsulfamoylbenzoesäureamide der nachfolgenden Formel (S-VII), die z.B. bekannt sind aus WO-A-99/16744,In particular, compounds of the acylsulfamoylbenzoic acid amide type represented by the following formula (S-VII), e.g. are known from WO-A-99/16744,
woπn R21 = Cyclo-Propyl und R22 = H ist (S3-1 = where R 21 = cyclopropyl and R 22 = H (S3-1 =
4-Cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzolsulfonamid; Cyprosulfamide);4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide; Cyprosulfamide);
R21 = Cyclo-Propyl und R22 = 5-CI ist (S3-2), R21 = Ethyl und R22 = H ist (S3-3), R21 = iso-Propyl und R22 = 5-CI ist (S3-4) und R21 = iso-Propyl und R22 = H ist (S3-5 =R 21 = cyclopropyl and R 22 = 5-CI is (S3-2), R 21 = ethyl and R 22 = H is (S3-3), R 21 = iso-propyl and R 22 = 5-CI (S3-4) and R 21 = isopropyl and R 22 = H (S3-5 =
4-iso-propylaminocarbonyl-N-(2-methoxybenzoyl)benzolsulfonamid);4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide);
e) Verbindungen vom Typ der N-Acylsulfamoylphenylharnstoffe der Formel (S-VIII)1 die z.B. bekannt sind aus der EP-A-365484,e) compounds of the type of the N-acylsulfamoylphenylureas of the formula (S-VIII) 1 which are known, for example, from EP-A-365484,
worin wherein
A für einen Rest aus der Gruppe A for a rest of the group
Rα und Rß unabhängig voneinander für Wasserstoff, d-Ce-Alkyl, C3-Cs-CyClOaI kyl, C3-C6-Alkenyl, C3-C6-Al kinyl,R α and R ß independently hydrogen, d-Ce-alkyl, alkyl-C 3 -Cs CyClOaI, C 3 -C 6 alkenyl, C 3 -C 6 kinyl Al,
oder durch C1-C4-AIkOXy oder or by C 1 -C 4 -alkoxy or
substituiertes C1-C4-AIkOXy, oder Rα und Rß gemeinsam für eine C4-C6-Alkylenbrücke oder eine durch Sauerstoff, Schwefel, SO, SO2, NH oder -N(CrC4-Alkyl)- unterbrochene C4-C6- Alkylenbrücke,substituted C 1 -C 4 -alkoxy, or R α and R ß together are a C 4 -C 6 alkylene or by oxygen, sulfur, SO, SO 2, NH or -N (C r C 4 alkyl) - interrupted C 4 -C 6 - alkylene bridge,
Rγ für Wasserstoff oder Ci-C4-Alkyl,R γ is hydrogen or C 1 -C 4 -alkyl,
Ra und Rb unabhängig voneinander für Wasserstoff, Halogen, Cyan, Nitro, Trifluormethyl, CrC4-Alkyl, C1-C4-AIkOXy, CrC4-Alkylthio, CrC4-Alkylsulfinyl,R a and R b independently represent hydrogen, halogen, cyano, nitro, trifluoromethyl, -C 4 alkyl, C 1 -C 4 -alkoxy, C r C 4 alkylthio, C r C 4 alkylsulfinyl,
CrOrAlkylsulfonyl, -COORj, -CONRkRm, -COR", -SO2NRkRm oder -OSO2-C1- C4-Alkyl, oder Ra und Rb gemeinsam für eine C3-C4-Alkylenbrücke, die durch Halogen oder C-ι-C4-Alkyl substituiert sein kann, oder eine C3-C4- Alkenylenbrücke, die durch Halogen oder C-ι-C4-Alkyl substituiert sein kann, oder eine C4-Alkadienylenbrücke, die durch Halogen oder CrC4-Alkyl substituiert sein kann, undCrOr alkylsulfonyl, -COOR j , -CONR k R m , -COR ", -SO 2 NR k R m or -OSO 2 -C 1 - C 4 alkyl, or R a and R b together represent a C 3 -C 4 alkylene bridge which is 4 alkyl may be substituted by halogen or C-ι-C, or a C 3 -C 4 - alkenylene, which may be substituted by halogen or C-ι-C 4 alkyl, or a C 4 - Alkadienylene bridge, which may be substituted by halogen or C 1 -C 4 -alkyl, and
R9 und Rh unabhängig voneinander für Wasserstoff, Halogen, Ci-C4-Alkyl, Trifluormethyl, Methoxy, Methylthio oder -COOR' stehen, wobeiR 9 and R h independently of one another represent hydrogen, halogen, C 1 -C 4 -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ', where
Rc Wasserstoff, Halogen, C1-C4-AIkVl oder Methoxy, Rd Wasserstoff, Halogen, Nitro, Ci-C4-Alkyl, CrC4-Alkoxy, CrC4-Alkylthio, C1-C4-R c is hydrogen, halogen, C 1 -C 4 -alkyl or methoxy, R d is hydrogen, halogen, nitro, Ci-C 4 alkyl, -C 4 alkoxy, -C 4 alkylthio, C 1 -C 4 -
Alkylsulfinyl, d-C-j-Alkylsulfonyl, -COORJ oder -CONRkRm, Re Wasserstoff, Halogen, Ci-C4-Alkyl, -COORj, Trifluormethyl oder Methoxy, oderAlkylsulfinyl, dCj-alkylsulfonyl, -COOR J or -CONR k R m , R e is hydrogen, halogen, Ci-C 4 alkyl, -COOR j , trifluoromethyl or methoxy, or
Rd und Re gemeinsam für eine C3-C4-Alkylenbrücke, Rf Wasserstoff, Halogen oder CrC4-Alkyl,R d and R e together represent a C 3 -C 4 -alkylene bridge, R f is hydrogen, halogen or C 1 -C 4 -alkyl,
Rx und Rγ unabhängig voneinander Wasserstoff, Halogen, d-C4-Alkyl, Ci-C4-R x and R γ independently represent hydrogen, halogen, C 4 alkyl, Ci-C 4 -
Alkoxy, CrC4-Alkylthio, -COOR4, Trifluormethyl, Nitro oder Cyan, RJ, Rk und Rm unabhängig voneinander Wasserstoff oder C-ι-C4-Alkyl, Rk und Rm gemeinsam eine C4-C6-Alkylenbrücke oder eine durch Sauerstoff, NH oder -N(CrC4-Alkyl)- unterbrochene Cj-Cβ-Alkylenbrücke, undAlkoxy, C r C 4 alkylthio, -COOR 4, trifluoromethyl, nitro or cyano, R J, R k and R m are independently hydrogen or C-ι-C 4 alkyl, R k and R m together form a C 4 - C 6 alkylene bridge or an interrupted by oxygen, NH or -N (C 1 -C 4 alkyl) - Cj-Cβ-alkylene bridge, and
Rn CrC4-Alkyl, Phenyl oder durch Halogen, Ci-C4-Alkyl, Methoxy, Nitro oderR n is C 1 -C 4 -alkyl, phenyl or by halogen, C 1 -C 4 -alkyl, methoxy, nitro or
Trifluormethyl substituiertes Phenyl bedeuten; vorzugsweise Safener der Formel (S-VIII) sindTrifluoromethyl substituted phenyl; preferably safeners of the formula (S-VIII)
1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylharnstoff, 1 -[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylharnstoff,1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea,
1-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylharnstoff,1- [4- (N-4,5-Dimethylbenzoylsulfamoyl) phenyl] -3-methyl-urea,
1-[4-(N-Naphthoylsulfamoyl)phenyl]-3,3-dimethylharnstoff, einschließlich der Stereoisomeren und der in der Landwirtschaft gebräuchlichen Salze.1- [4- (N-Naphthoylsulfamoyl) phenyl] -3,3-dimethylurea, including the stereoisomers and the salts commonly used in agriculture.
Sofern es im Einzelnen nicht anders definiert wird, gelten für die Reste in den Formeln zu (S-Il) bis (S-VIII) im Allgemeinen die folgenden Definitionen. Die Reste Alkyl, Alkoxy, Haloalkyl, Haloalkoxy, Alkylamino und Alkylthio sowie die entsprechenden ungesättigten und/oder substituierten Reste können im Kohlenstoffgerüst jeweils geradkettig oder verzweigt sein.Unless otherwise defined in detail, the following definitions generally apply to the radicals in the formulas (S-II) to (S-VIII). The radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals can each be straight-chain or branched in the carbon skeleton.
Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw. haben vorzugsweise 1 bis 4 C-Atome und, bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl. Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten Reste; Alkenyl bedeutet z.B. AIIyI, 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 und 1-Methyl-but-2-en-1-yl. Alkinyl bedeutet z.B. Propargyl, But-2-in-1-yl, But-3-in-1-yl, 1-Methyl-but-3-in-1-yl. "(Ci-C4)-Alkyl" ist die Kurzschreibweise für Alkyl mit 1 bis 4 C-Atomen; entsprechendes gilt für andere allgemeine Restedefinitionen mit in Klammern angegebenen Bereichen für die mögliche Anzahl von C-Atomen.Alkyl radicals, even in the composite meanings such as alkoxy, haloalkyl, etc., preferably have 1 to 4 carbon atoms and, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl. Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl is, 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-but-2-en-1-yl. Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. "(C 1 -C 4 ) -alkyl" is the Short for alkyl having 1 to 4 carbon atoms; the same applies to other general remainder definitions with bracketed ranges for the possible number of C atoms.
Cycloalkyl bedeutet bevorzugt einen cyclischen Alkylrest mit 3 bis 8, vorzugsweise 3 bis 7, besonders bevorzugt 3 bis 6 C-Atomen, beispielsweise Cyclopropyl,Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, particularly preferably 3 to 6, C atoms, for example cyclopropyl,
Cyclobutyl, Cyclopentyl und Cyclohexyl. Cycloalkenyl und Cycloalkinyl bezeichnen entsprechende ungesättigte Verbindungen.Cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl refer to corresponding unsaturated compounds.
Halogen bedeutet Fluor, Chlor, Brom oder lod. Haloalkyl, Haloalkenyl und Haloalkinyl bedeuten durch Halogen, vorzugsweise durch Fluor, Chlor und/oder Brom, insbesondere durch Fluor oder Chlor, teilweise oder vollständig substituiertes Alkyl, Alkenyl oder Alkinyl, z.B. CF3, CHF2, CH2F, CF2CF3, CH2CHFCI, CCI3, CHCI2, CH2CH2CI. Haloalkoxy ist z.B. OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 und OCH2CH2CI. Entsprechendes gilt für sonstige Halogen substituierte Reste. Ein Kohlenwasserstoffrest kann ein aromatischer oder ein aliphatischer Kohlenwasserstoffrest sein, wobei ein aliphatischer Kohlenwasserstoffrest im allgemeinen ein geradkettiger oder verzweigter gesättigter oder ungesättigter Kohlenwasserstoffrest ist, vorzugsweise mit 1 bis 18, besonders bevorzugt 1 bis 12 C-Atomen, z.B. Alkyl, Alkenyl oder Alkinyl. Vorzugsweise bedeutet aliphatischer Kohlenwasserstoffrest Alkyl, Alkenyl oder Alkinyl mit bis zu 12 C-Atomen; entsprechendes gilt für einen aliphatischen Kohlenwasserstoffrest in einem Kohlenwasserstoffoxyrest.Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or fully substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF 2 CF 3 , CH 2 CHFCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl. Haloalkoxy is eg OCF 3 , OCHF 2 , OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl. The same applies to other halogen-substituted radicals. A hydrocarbon radical can be an aromatic or an aliphatic hydrocarbon radical, where an aliphatic hydrocarbon radical is generally a straight-chain or branched saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, particularly preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl. Preferably, aliphatic hydrocarbon radical alkyl, alkenyl or alkynyl having up to 12 carbon atoms; the same applies to an aliphatic hydrocarbon radical in a Kohlenwasserstoffoxyrest.
Aryl ist im allgemeinen ein mono-, bi- oder polycyclisches aromatisches System mit vorzugsweise 6-20 C-Atomen, bevorzugt 6 bis 14 C-Atomen, besonders bevorzugt 6 bis 10 C-Atomen, z.B. Phenyl, Naphthyl, Tetrahydronaphthyl, Indenyl, Indanyl, Pentalenyl und Fluorenyl, besonders bevorzugt Phenyl.Aryl is generally a mono-, bi- or polycyclic aromatic system having preferably 6-20 C atoms, preferably 6 to 14 C atoms, more preferably 6 to 10 C atoms, e.g. Phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl and fluorenyl, more preferably phenyl.
Heterocyclischer Ring, heterocyclischer Rest oder Heterocyclyl bedeutet ein mono-, bi- oder polycyclisches Ringsystem, das gesättigt, ungesättigt und/oder aromatisch ist und eine oder mehrere, vorzugsweise 1 bis 4, Heteroatome, vorzugsweise aus der Gruppe N, S und O, enthält. Bevorzugt sind gesättigte Heterocyclen mit 3 bis 7 Ringatomen und einem oder zwei Heteroatomen aus der Gruppe N, O und S, wobei die Chalcogene nicht benachbart sind. Besonders bevorzugt sind monocyclische Ringe mit 3 bis 7 Ringatomen und einem Heteroatom aus der Gruppe N, O und S, sowie Morpholin, Dioxolan, Piperazin, Imidazolin und Oxazolidin. Ganz besonders bevorzugte gesättigte Heterocyclen sind Oxiran, Pyrrolidon, Morpholin und Tetrahydrofuran. Bevorzugt sind auch teilweise ungesättigte Heterocyclen mit 5 bis 7 Ringatomen und einem oder zwei Heteroatomen aus der Gruppe N, O und S. Besonders bevorzugt sind teilweise ungesättigte Heterocyclen mit 5 bis 6 Ringatomen und einem Heteroatom aus der Gruppe N, O und S. Ganz besonders bevorzugte teilweise ungesättigte Heterocyclen sind Pyrazolin, Imidazolin und Isoxazolin. Ebenso bevorzugt ist Heteroaryl, z.B. mono- oder bicyclische aromatische Heterocyclen mit 5 bis 6 Ringatomen, die ein bis vier Heteroatome aus der Gruppe N, O, S enthalten, wobei die Chalcogene nicht benachbart sind. Besonders bevorzugt sind monocyclische aromatische Heterocyclen mit 5 bis 6 Ringatomen, die ein Heteroatom aus der Gruppe, N, O und S enthalten, sowie Pyrimidin, Pyrazin, Pyridazin, Oxazol, Thiazol, Thiadiazol, Oxadiazol, Pyrazol, Triazol und Isoxazol. Ganz besonders bevorzugt sind Pyrazol, Thiazol, Triazol und Furan.Heterocyclic ring, heterocyclic radical or heterocyclyl means a mono-, bi- or polycyclic ring system which is saturated, unsaturated and / or aromatic and contains one or more, preferably 1 to 4, heteroatoms, preferably from the group N, S and O. , Preferred are saturated heterocycles having 3 to 7 ring atoms and one or two heteroatoms from the group N, O and S, wherein the chalcogens are not adjacent. Particularly preferred are monocyclic rings having 3 to 7 ring atoms and a heteroatom from the group N, O and S, as well as morpholine, dioxolane, piperazine, imidazoline and oxazolidine. Very particularly preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran. Also preferred are partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms from the group N, O and S. Particularly preferred are partially unsaturated heterocycles having 5 to 6 ring atoms and one heteroatom from the group N, O and S. Very particular preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline. Also preferred is heteroaryl, for example mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms containing one to four heteroatoms from the group N, O, S, wherein the chalcogens are not adjacent. Particularly preferred are monocyclic aromatic heterocycles having 5 to 6 ring atoms which contain a heteroatom from the group, N, O and S, and pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and isoxazole. Very particular preference is given to pyrazole, thiazole, triazole and furan.
Substituierte Reste, wie substituierte Kohlenwasserstoffreste, z.B. substituiertes Alkyl, Alkenyl, Alkinyl, Aryl wie Phenyl und Arylalkyl wie Benzyl, oder substituiertes Heterocyclyl, bedeuten einen vom unsubstituierten Grundkörper abgeleiteten substituierten Rest, wobei die Substituenten vorzugsweise einen oder mehrere, vorzugsweise 1 , 2 oder 3, im Falle von Cl und F auch bis zur maximal möglichen Anzahl, Substituenten aus der Gruppe Halogen, Alkoxy, Haloalkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy, Cyano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyl, Mono- und Dialkylaminocarbonyl, substituiertes Amino wie Acylamino, Mono- und Dialkylamino und Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl und, im Falle cyclischer Reste, auch Alkyl und Haloalkyl sowie den genannten gesättigten kohlenwasserstoffhaltigen Substituenten entsprechende ungesättigte aliphatische Substituenten, vorzugsweise Alkenyl, Alkinyl, Alkenyloxy, Alkinyloxy, bedeuten. Bei Resten mit C-Atomen sind solche mit 1 bis 4 C-Atomen, insbesondere 1 oder 2 C-Atomen, bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor oder Chlor, (CrC4)Alkyl, vorzugsweise Methyl oder Ethyl, (CrC^Haloalkyl, vorzugsweise Trifluormethyl, (Ci -C4)Alkoxy, vorzugsweise Methoxy oder Ethoxy, (Ci-C4)Haloalkoxy, Nitro und Cyano. Besonders bevorzugt sind dabei die Substituenten Methyl, Methoxy und Chlor.Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, such as phenyl and arylalkyl, such as benzyl, or substituted heterocyclyl, represent a substituted radical derived from the unsubstituted radical, where the substituents are preferably one or more, preferably 1, 2 or 3 , in the case of Cl and F also up to the maximum possible number, substituents 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, in the case of cyclic radicals, also alkyl and haloalkyl and said saturated hydrocarbon-containing substituents corresponding unsaturated aliphatic substituents, preferably alkenyl, alkynyl, alkenyloxy, alkynyloxy , For radicals with C atoms, those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. As a rule, preference is given to substituents from the group halogen, for example fluorine or chlorine, (C 1 -C 4 ) -alkyl, preferably methyl or ethyl, (C 1 -C 4 -haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) -alkoxy, preferably methoxy or ethoxy, C 4 ) haloalkoxy, nitro and Cyano. Particularly preferred are the substituents methyl, methoxy and chlorine.
Mono- oder disubstituiertes Amino bedeutet einen chemisch stabilen Rest aus der Gruppe der substituierten Aminoreste, welche beispielsweise durch einen oder zwei gleiche oder verschiedene Reste aus der Gruppe Alkyl, Alkoxy, Acyl und Aryl N-substituiert sind; vorzugsweise Monoalkylamino, Dialkylamino, Acylamino, Arylamino, N-Alkyl-N-Arylamino sowie N-Heterocyclen. Dabei sind Alkylreste mit 1 bis 4 C-Atomen bevorzugt. Aryl ist dabei vorzugsweise Phenyl. Substituiertes Aryl ist dabei vorzugsweise substituiertes Phenyl. Für Acyl gilt dabei die weiter unten genannte Definition, vorzugsweise (CrC4)Alkanoyl. Entsprechendes gilt für substituiertes Hydroxylamino oder Hydrazino.Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are N-substituted by, for example, one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles. In this case, alkyl radicals having 1 to 4 carbon atoms are preferred. Aryl is preferably phenyl. Substituted aryl is preferably substituted phenyl. This is true for acyl the definition mentioned further below applies, preferably (CrC 4) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
Gegebenenfalls substituiertes Phenyl ist vorzugsweise Phenyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach, bei Halogen wie Cl und F auch bis zu fünffach, durch gleiche oder verschiedene Reste aus der Gruppe Halogen, (CrC4)Alkyl, (CrC4)Alkoxy, (CrC4)Haloalkyl, (CrC4)Haloalkoxy und Nitro substituiert ist, z.B. o-, m- und p-Tolyl, Dimethylphenyle, 2-, 3- und 4-Chlorphenyl, 2-, 3- und 4-Trifluor- und -Trichlorphenyl, 2,4-, 3,5-, 2,5- und 2,3-Dichlorphenyl, o-, m- und p-Methoxyphenyl. Ein Acylrest bedeutet den Rest einer organischen Säure mit vorzugsweise bis zu 6 C-Atomen, z.B. den Rest einer Carbonsäure und Reste davon abgeleiteter Säuren wie der Thiocarbonsäure, gegebenenfalls N-substituierter Iminocarbonsäuren, oder der Rest von Kohlensäuremonoestern, gegebenenfalls N-substituierter Carbaminsäuren, Sulfonsäuren, Sulfinsäuren, Phosphonsäuren, Phosphinsäuren. Acyl bedeutet beispielsweise Formyl, Alkylcarbonyl, wie (CrC4-Alkyl)-carbonyl, Phenylcarbonyl, wobei der Phenylring substituiert sein kann, z.B. wie oben fürOptionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, in halogens such as Cl and F also up to five times, by identical or different radicals from the group halogen, (C r C 4 ) alkyl, ( C r C 4 ) alkoxy, (C 1 -C 4 ) haloalkyl, (C r C 4 ) haloalkoxy and nitro, 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. An acyl radical is the radical of an organic acid having preferably up to 6 C atoms, for example the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the radical of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids , Sulfinic acids, phosphonic acids, phosphinic acids. Acyl, for example, formyl, alkylcarbonyl, such as (C r C 4 alkyl) carbonyl, phenylcarbonyl, wherein the phenyl ring may be substituted, for example as above
Phenyl angegeben, oder Alkyloxycarbonyl, Phenyloxycarbonyl, Benzyloxycarbonyl, Alkylsulfonyl, Alkylsulfinyl oder N-Alkyl-1-iminoalkyl.Phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl or N-alkyl-1-iminoalkyl.
Von den Formeln (S-Il) bis (S-VIII) umfasst sind auch alle Stereoisomeren, welche die gleiche topologische Verknüpfung der Atome aufweisen, und deren Gemische. Solche Verbindungen enthalten ein oder mehrere asymmetrische C-Atome oder auch Doppelbindungen, die in den allgemeinen Formeln nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere, können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.Also encompassed by the formulas (S-II) to (S-VIII) are all stereoisomers which have the same topological linkage of the atoms, and mixtures thereof. Such compounds contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formulas. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
Die Verbindungen der Formel (S-Il) sind z.B. aus EP-A-0333131 (ZA-89/1960), EP-A-0269806 (US 4,891 ,057), EP-A-0346620 (AU-A-89/34951 ), EP-A-0174562, EP-A-0346620 (WO-A-91 /08202), WO-A-91/07874 oder WO-A-95/07897 (ZA 94/7120) und der dort zitierten Literatur bekannt oder können nach oder analog den dort beschriebenen Verfahren hergestellt werden. Die Verbindungen der Formel (S- III) sind aus EP-A-0086750, EP-A-094349 (US 4,902,340), EP-A-0191736 (US 4,881 ,966) und EP-A-0492366 und dort zitierter Literatur bekannt oder können nach oder analog den dort beschriebenen Verfahren hergestellt werden. Einige Verbindungen sind ferner in EP-A-0582198 und WO-A-02/34048 beschrieben. Die Verbindungen der Formel (S-IV) sind aus zahlreichen Patentanmeldungen bekannt, beispielsweise US 4,021 ,224 und US 4,021 ,229. Verbindungen der Untergruppe b) sind weiterhin aus CN-A-87/102789, EP-A-365484 sowie aus "The Pesticide Manual", 11. bis 13. Auflage, British Crop Protection Council and the Royal Society of Chemistry (1997), bekannt. Die Verbindungen der Untergruppe c) sind in der WO- A-97/45016, die der Untergruppe d) in der WO-A-99/16744 (insbesondere in EP-A- 365484) beschrieben. Die zitierten Schriften enthalten ausführliche Angaben zu Herstellungsverfahren und Ausgangsmaterialien und nennen bevorzugte Verbindungen. Auf diese Schriften wird ausdrücklich Bezug genommen, sie gelten durch Zitat als Bestandteil dieser Beschreibung.The compounds of formula (S-II) are e.g. from EP-A-0333131 (ZA-89/1960), EP-A-0269806 (US 4,891,057), EP-A-0346620 (AU-A-89/34951), EP-A-0174562, EP-A No. 0346620 (WO-A-91/08202), WO-A-91/07874 or WO-A-95/07897 (ZA 94/7120) and the literature cited therein, or can be prepared by or analogously to the processes described therein , The compounds of the formula (S-III) are known from EP-A-0086750, EP-A-094349 (US 4,902,340), EP-A-0191736 (US 4,881,966) and EP-A-0492366 and literature cited therein or US Pat can be prepared according to or analogously to the methods described therein. Some compounds are further described in EP-A-0582198 and WO-A-02/34048. The compounds of formula (S-IV) are known from numerous patent applications, for example US 4,021,224 and US 4,021,229. Compounds of subgroup b) are further from CN-A-87/102789, EP-A-365484 and from "The Pesticide Manual", 11th to 13th edition, British Crop Protection Council and the Royal Society of Chemistry (1997), known. The compounds of subgroup c) are described in WO-A-97/45016, those of subgroup d) in WO-A-99/16744 (in particular in EP-A-365484). The cited documents contain detailed information on preparation processes and starting materials and name preferred compounds. These documents are expressly referred to, they are by quotation as part of this description.
Die Safener der vorstehenden Gruppen a) bis e) reduzieren oder unterbinden phytotoxische Effekte, die beim Einsatz der herbiziden Mittel gemäß der Erfindung in Nutzpflanzenkulturen auftreten können, ohne die Wirksamkeit der Herbizide gegen Schadpflanzen zu beeinträchtigen. Hierdurch kann das Einsatzgebiet der Herbizide erheblich erweitert werden und insbesondere ist durch die Verwendung von Safenern der Einsatz von Herbiziden, die bislang nur beschränkt oder mit nicht ausreichendem Erfolg eingesetzt werden konnten, d.h. von Kombinationen, die ohne Safener in niedrigen Dosierungen mit wenig Breitenwirkung zu nicht ausreichender Kontrolle der Schadpflanzen führten.The safeners of the above groups a) to e) reduce or prevent the phytotoxic effects which can occur when using the herbicidal compositions according to the invention in crops without impairing the effectiveness of the herbicides against harmful plants. As a result, the field of application of the herbicides can be significantly extended and in particular by the use of safeners, the use of herbicides, which have so far only limited or could be used with insufficient success, ie of combinations without Safener in low dosages with little broader effect led to insufficient control of harmful plants.
Besonders bevorzugt kommen sind als Safener in den erfindungsgemäßen Formulierungen unter anderem: 4-Dichloracetyl-1-oxa-4-aza-spiro[4.5]-decan (AD- 67), 1 -Dichloracetyl-hexahydro-3,3,8a-trimethylpyrrolo[1 ,2-a]-pyrimidin-6(2H)-on (Dicyclonon, BAS-145138), 4-Dichloracetyl-3,4-dihydro-3-methyl-2H-1 ,4-benzoxazin (Benoxacor), Cloquintocet, 5-Chlor-chinolin-8-oxy-essigsäure-(1 -methyl-hexylester) (Cloquintocet-mexyl), α-(Cyanomethoxyimino)-phenylacetonitril (Cyometrinil), 2,2- Dichlor-N-(2-oxo-2-(2-propenylamino)-ethyl)-N-(2-propenyl)-acetamid (DKA-24), 2,2- Dichlor-N,N-di-2-propenyl-acetamid (Dichlormid), N-(4-Methyl-phenyl)-N'-(1 -methyl- 1-phenyl-ethyl)-harnstoff (Dymron), 4,6-Dichlor-2-phenyl-pyrimidin (Fenclorim), 1- (2,4-Dichlor-phenyl)-5-trichlormethyl-1 H-1 ,2,4-triazol-3-carbonsäure-ethylester (Fenchlorazol-ethyl), 2-Chlor-4-trifluormethyl-thiazol-5-carbonsäure- phenylmethylester (Flurazole), 4-Chlor-N-(1 ,3-dioxolan-2-yl-methoxy)-α-trifluor- acetophenonoxim (Fluxofenim), 3-Dichloracetyl-5-(2-furanyl)-2,2-dimethyl-oxazolidin (Furilazole, MON-13900), Ethyl-4,5-dihydro-5,5-diphenyl-3-isoxazolcarboxylat (Isoxadifen-ethyl), Diethyl-1 -(2,4-dichlorphenyl)-4,5-dihydro-5-methyl-1 H-pyrazol-3,5- dicarboxylat (Mefenpyr-diethyl), 2-Dichlormethyl-2-methyl-1 ,3-dioxolan (MG-191), 1 ,8-Naphthalsäureanhydrid, α-(1 ,3-Dioxolan-2-yl-methoximino)-phenylacetonitril (Oxabetrinil), 2,2-Dichlor-N-(1 ,3-dioxolan-2-yl-methyl)-N-(2-propenyl)-acetamid (PPG-1292), 3-Dichloracetyl-2,2-dimethyl-oxazolidin (R-28725), 3-Dichloracetyl- 2,2,5-trimethyl-oxazolidin (R-29148), 1-(2-Chlor-phenyl)-5-phenyl-1 H-pyrazol-3- carbonsäure-methylester, 4-Cyclopropylaminocarbonyl-N-(2- methoxybenzoyl)benzolsulfonamid (Cyprosulfamide), 4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl)benzolsulfonamid und N-(2-Methoxy-benzoyl)-4-[(methylamino- carbonyl)-amino]-benzolsulfonamid.Particular preference is given as safeners in the formulations according to the invention, inter alia: 4-dichloroacetyl-1-oxa-4-aza-spiro [4.5] -decane (AD-67), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo [1,2-a] pyrimidine-6 (2H) -one (dicyclonone, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (Benoxacor), cloquintocet , 5-chloro-quinolin-8-oxy-acetic acid (1-methyl-hexyl ester) (cloquintocet-mexyl), α- (cyanomethoxyimino) -phenylacetonitrile (cyometrinil), 2,2-dichloro-N- (2-oxo) 2- (2-propenylamino) ethyl) -N- (2-propenyl) acetamide (DKA-24), 2,2-dichloro-N, N-di-2-propenyl-acetamide (dichloromid), N- ( 4-methyl-phenyl) -N '- (1-methyl-1-phenylethyl) -urea (Dymron), 4,6-dichloro-2-phenyl-pyrimidine (fenclorim), 1- (2,4-dichloro -phenyl) -5-trichloromethyl-1 H-1, 2,4-triazole-3-carboxylic acid ethyl ester (fenchlorazole-ethyl), 2-chloro-4-trifluoromethyl-thiazole-5-carboxylic acid phenylmethyl ester (flurazole), 4 -Chloro-N- (1,3-dioxolan-2-yl-methoxy) -α-trifluoroacetophenone oxime (Fluxofenim), 3-dichloroacetyl-5- (2-furanyl) -2,2-dimethyl-oxazolidine (furilazole, MON-13900), ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl), Diethyl 1 - (2,4-dichlorophenyl) -4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate (mefenpyr-diethyl), 2-dichloromethyl-2-methyl-1, 3 dioxolane (MG-191), 1,8-naphthalic anhydride, α- (1,3-dioxolan-2-yl-methoximino) -phenylacetonitrile (oxabetrinil), 2,2-dichloro-N- (1,3-dioxolane-2 -yl-methyl) -N- (2-propenyl) -acetamide (PPG-1292), 3-dichloroacetyl-2,2-dimethyl-oxazolidine (R-28725), 3-dichloroacetyl-2,2,5-trimethyl- oxazolidine (R-29148), methyl 1- (2-chloro-phenyl) -5-phenyl-1H-pyrazole-3-carboxylate, 4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide (cyprosulfamide), 4- iso -propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide and N- (2-methoxybenzoyl) -4 - [(methylaminocarbonyl) amino] benzenesulfonamide.
Ganz besonders bevorzugt sind die Safenern Mefenpyr-diethyl, Cloquintocet-mexyl, Isoxadifen-ethyl, 4-Cyclopropylaminocarbonyl-N-(2- methoxybenzoyl)benzolsulfonamid (Cyprosulfamide), 4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl)benzolsulfonamid oder Fenchlorazol-ethyl; insbesondere ganz besonders bevorzugt sind Mefenpyr-diethyl, Cloquintocet-mexyl oder Isoxadifen- ethyl.Very particular preference is given to the safeners mefenpyr-diethyl, cloquintocet-mexyl, isoxadifen-ethyl, 4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide (cyprosulfamide), 4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide or fenchlorazole ethyl; especially whole Particular preference is given to mefenpyr-diethyl, cloquintocet-mexyl or isoxadifen-ethyl.
Besondere Ausführungsformen der Erfindung sind das Verfahren zur Förderung der Penetration und dessen Verwendung, wobei TBEP in den erfindungsgemäßen Mengen (B) mit Mischungen von Herbiziden und Safener (A), entweder gleichzeitig oder sequentiell appliziert wird.Particular embodiments of the invention are the method for promoting the penetration and its use, wherein TBEP is applied in the amounts (B) according to the invention with mixtures of herbicides and safener (A), either simultaneously or sequentially.
Bevorzugte Herbizid-Safener-Mischungen sind Kombinationen der folgenden Verbindungen miteinander:Preferred herbicide-safener mixtures are combinations of the following compounds with one another:
a) Verbindungen, die als ACCase-lnhibitoren wirksam sind, wie Alloxydim, Butroxydim, Clethodim, Clodinafop-propargyl, Cycloxydim, Cyhalofop-butyl, Diclofop- methyl, Fenoxaprop, Fenoxaprop-ethyl, Fenoxaprop-P, Fenoxaprop-P-ethyl, Fluazifop, Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfop- etotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P- tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim, Tralkoxydim und Isoxapyrifop,a) compounds which are active as ACCase inhibitors, such as alloxydim, butroxydim, clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofopmethyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop , Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfopetotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim, Tralkoxydim and isoxapyrifop,
b) Verbindungen, die als p-Hydroxyphenyl pyruvate dioxygenase (HPPD)-Inhibitoren wirksam sind, wie Benzobicyclon, Benzofenap, Isoxaflutole und dessen Diketonitrile, Mesotrione, Pyrazolynate, Pyrazoxyfen, Sulcotrione und Isoxachlortole,b) compounds which are effective as p-hydroxyphenyl pyruvate dioxygenase (HPPD) inhibitors, such as benzobicyclone, benzofenap, isoxaflutole and its diketronitrile, mesotrione, pyrazolynate, pyrazoxyfen, sulcotrione and isoxachlortole,
c) Verbindungen verschiedener Wirkstoffgruppen, wie Atrazin, Acetochlor, Aclonifen, Alachlor, Amidochlor, Amidosulfuron, Azimsulfuron, Bentazon, Bensulfuron(-methyl), Bromoxynil(-octanoat/-heptanoat), Butachlor, Bispyribac, Chlorsulfuron, Chlorimuron, Clomazone, Clopyralid, Cinosulfuron, Cyclosulfamuron, 2,4-D-Ester, 2,4-DB-Ester, 2,4-DP-Ester, CMPP-Ester, MCPA-Ester, MCPB, EPTC, Desmedipham, Diflufenican, Dicamba, Ethoxysulfuron, Ethofumesat, Flazasulfuron, Florasulam, Flucarbazone, Flumetsulam, Flufenacet, Fluoroglykofen, Fluroxypyr, Flupyrsulfuron, Foramsulfuron, Flumioxazin, Flumiclorac, Fomesafen, Glufosinate, Glyphosate, Imazapyr, Imazosulfuron, lodosulfuron, lodosulfuron-methyl, loxynil(-octanoat), Lactofen, Halosulfuron, Imazamox, Imazapic, Imazapyr, Imazethapyr, Imazaquin, Metosulam, Mesosulfuron(-methyl), (S-)Metolachlor, Metsulfuron-methyl, Metamitron, Nicosulfuron, Oxyfluorfen, Pendimethalin, Phenmedipham, Picloram, Pinoxaden, Primisulfuron-methyl, Prosulfuron, Propanil, Propoxycarbazone, Pyrazosulfuron(-methyl), Rimsulfuron, Sulfentrazone, Sulfosulfuron, Sulfometuron, Terbuthylazin, Thifensulfuron, Triasulfuron, Tribenuron, Triclopyr, Triflusulfuron- methyl, Trifluralin, Tritosulfuron, Topramezone, Oxazinon, Oxadiargyl, Metribuzin, und deren Salze, z.B. die Natriumsalze.c) Compounds of various active ingredient groups, such as atrazine, acetochlor, aclonifen, alachlor, amidochlor, amidosulfuron, azimsulfuron, bentazone, bensulfuron (-methyl), bromoxynil (-octanoate / -heptanoate), butachlor, bispyribac, chlorosulfuron, chlorimuron, clomazone, clopyralid, Cinosulfuron, cyclosulfamuron, 2,4-D-ester, 2,4-DB-ester, 2,4-DP-ester, CMPP-ester, MCPA-ester, MCPB, EPTC, desmedipham, diflufenican, dicamba, ethoxysulfuron, ethofumesate, Flazasulfuron, florasulam, flucarbazone, flumetsulam, flufenacet, fluoroglycofen, fluroxypyr, flupyrsulfuron, foramsulfuron, flumioxazine, flumiclorac, fomesafen, glufosinate, glyphosate, imazapyr, imazosulfuron, lodosulfuron, lodosulfuron-methyl, loxynil (-octanoate), Lactofen, halosulfuron, imazamox, imazapic, imazapyr, imazethapyr, imazaquin, metosulam, mesosulfuron (-methyl), (S) -metolachlor, metsulfuron-methyl, metamitron, nicosulfuron, oxyfluorfen, pendimethalin, phenmedipham, picloram, pinoxaden, primisulfuron-methyl, Prosulfuron, propanil, propoxycarbazone, pyrazosulfuron (-methyl), rimsulfuron, sulfentrazone, sulfosulfuron, sulfometuron, terbuthylazine, thifensulfuron, triasulfuron, tribenuron, triclopyr, triflusulfuron-methyl, trifluralin, tritosulfuron, toramezone, oxazinone, oxadiargyl, metribuzin, and their salts, eg the sodium salts.
d) Verbindungen, die als Safener wirksam sind, wie AD 67 (4-(dichloroacetyl)-1-oxa- 4-azaspiro[4.5]decane), Benoxacor, CL 304,415 (4-carboxymethylchroman-4- carboxylic acid), Cloquintocet, Cloquintocet-mexyl, Cyprosulfamide, Dichlormid, Dicyclonon, DKA-24 (N1 ,N2-diallyl-N2-dichloroacetylglycinamide), Fenchlorazole, Fenchlorazole-ethyl, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen-ethyl, Mefenpyr-diethyl, MG 191 (2-dichloromethyl-2-methyl-1 ,3-dioxolane),d) compounds which act as safeners, such as AD 67 (4- (dichloroacetyl) -1-oxa-4-azaspiro [4.5] decane), benoxacor, CL 304,415 (4-carboxymethylchroman-4-carboxylic acid), cloquintocet, Cloquintocet-mexyl, cyprosulfamides, dichloromide, dicyclonon, DKA-24 (N1, N2-diallyl-N2-dichloroacetylglycine amides), fenchlorazoles, fenchlorazoles-ethyl, fenclorim, flurazoles, fluxofenim, furilazoles, isoxadifen-ethyl, mefenpyr-diethyl, MW 191 ( 2-dichloromethyl-2-methyl-1,3-dioxolane),
Naphthalsäureanhydrid (naphthalene-1 ,8-dicarboxylic anhydride), Oxabetrinil and Tl- 35 (1-dichloroacetylazepane).Naphthalic anhydride (naphthalene-1,8-dicarboxylic anhydride), oxabetrinil and Tl-35 (1-dichloroacetylazepane).
In einer weiteren Ausführungsform können z.B. verschiedene Herbizide miteinander kombiniert werden, z.B. Fenoxaprop-p-ethyl + loxynil-octanoat, Diclofop-methyl + Bromoxynil-octanoat, CMPP + Bromoxynil-octanoat, MCPA + loxynil-octanoat, Bromoxynil-octanoat + Bromoxynil-heptanoat, Bromoxynil-octanoat + Bromoxynil- heptanoat + MCPA, Bromoxynil-octanoat + Bromoxynil-heptanoat+ 2,4-D, Phenmedipham + Desmedipham, Phenmedipham + Desmedipham + Ethofumesate, Metamitron + Ethofumesate, Phenmedipham + Ethofumesate + Metamitron,In another embodiment, e.g. different herbicides are combined, e.g. Fenoxaprop-p-ethyl + loxyniloctanoate, diclofopmethyl + bromoxyniloctanoate, CMPP + bromoxyniloctanoate, MCPA + loxyniloctanoate, bromoxyniloctanoate + bromoxynil heptanoate, bromoxyniloctanoate + bromoxynilheptanoate + MCPA, bromoxynil octanoate + bromoxynil heptanoate + 2,4-D, phenmedipham + desmedipham, phenmedipham + desmedipham + ethofumesate, metamitron + ethofumesate, phenmedipham + ethofumesate + metamitron,
Fenoxaprop-p-ethyl + lodosulfuron-methyl-natrium, Fenoxaprop-p-ethyl + Diclofop- methyl, Fenoxaprop-p-ethyl + lodosulfuron-methyl-natrium + Diclofop-methyl.Fenoxaprop-p-ethyl + iodosulfuron-methyl-sodium, fenoxaprop-p-ethyl + diclofop-methyl, fenoxaprop-p-ethyl + iodosulfuron-methyl-sodium + diclofop-methyl.
Als besonders bevorzugt sind die Kombinationen aus: Foramsulfuron + lodosulfuron- methyl-sodium + Isoxadifen-ethyl, lodosulfuron-methyl-sodium + Isoxadifen-ethyl, Foramsulfuron + Isoxadifen-ethyl, Fenoxaprop-P-ethyl + Ethoxysulfuron + Isoxadifen-ethyl, Ethoxysulfuron + Isoxadifen-ethyl, Fenoxaprop-P-ethyl + Isoxadifen-ethyl, lodosulfuron-methyl-sodium + Mesosulfuron-methyl + Mefenpyr- diethyl, Mesosulfuron-methyl + Mefenpyr-diethyl, lodosulfuron-methyl-sodium + Mefenpyr-diethyl, Fenoxaprop-P-ethyl + Mefenpyr-diethyl, Fenoxaprop-P-ethyl + Diclofop-methyl + Mefenpyr-diethyl, Diclofop-methyl + Mefenpyr-diethyl, Diclofop- methyl + Sethoxydim + Mefenpyr-diethyl, Sethoxydim + Mefenpyr-diethyl,The combinations of foramsulfuron + iodosulfuron-methyl-sodium + isoxadifen-ethyl, iodosulfuron-methyl-sodium + isoxadifen-ethyl, foramsulfuron + isoxadifen-ethyl, fenoxaprop-P-ethyl + ethoxysulfuron + isoxadifen-ethyl, ethoxysulfuron + are particularly preferred Isoxadifen-ethyl, fenoxaprop-P-ethyl + Isoxadifen-ethyl, iodosulfuron-methyl-sodium + mesosulfuron-methyl + mefenpyr-diethyl, mesosulfuron-methyl + mefenpyr-diethyl, iodosulfuron-methyl-sodium + mefenpyr-diethyl, fenoxaprop-P-ethyl + mefenpyr-diethyl, fenoxaprop-P ethyl + diclofop-methyl + mefenpyr-diethyl, diclofop-methyl + mefenpyr-diethyl, diclofopmethyl + sethoxydim + mefenpyr-diethyl, sethoxydim + mefenpyr-diethyl,
Fenoxaprop-P-ethyl + Isoproturon + Mefenpyr-diethyl, Isoproturon + Mefenpyr- diethyl, Clodinafop-propargyl + Cloquintocet-mexyl, Fenoxaprop-ethyl + Fenchlorazole-ethyl, Fenoxaprop-P-ethyl + Fenchlorazole-ethyl, Flucarbazone + Cyprosulfamide, Foramsulfuron + Cyprosulfamide, lodosulfuron(-methyl) + Cyprosulfamide, Metosulam + Cyprosulfamide, Metsulfuron(-methyl) + Cyprosulfamide, Nicosulfuron + Cyprosulfamide, Primisulfuron(. methyl) + Cyprosulfamide, Prosulfuron + Cyprosulfamide, Thifensulfuron + Cyprosulfamide, Tribenuron + Cyprosulfamide, Cloransulam-methyl + Cyprosulfamide, Chlorimuron + Cyprosulfamide, Ethoxysulfuron + Cyprosulfamide, Flazasulfuron + Cyprosulfamide, Florasulam + Cyprosulfamide, Flumetsulam + Cyprosulfamide, Halosulfuron +Fenoxaprop-P-ethyl + isoproturon + mefenpyr-diethyl, isoproturon + mefenpyr-diethyl, clodinafop-propargyl + cloquintocet-mexyl, fenoxaprop-ethyl + fenchlorazole-ethyl, fenoxaprop-P-ethyl + fenchlorazole-ethyl, flucarbazone + cyprosulfamide, foramsulfuron + Cyprosulfamides, iodosulfuron (-methyl) + Cyprosulfamide, Metosulam + Cyprosulfamide, Metsulfuron (-methyl) + Cyprosulfamide, Nicosulfuron + Cyprosulfamide, Primisulfuron (.methyl) + Cyprosulfamide, Prosulfuron + Cyprosulfamide, Thifensulfuron + Cyprosulfamide, Tribenuron + Cyprosulfamide, Cloransulam-methyl + Cyprosulfamide, Chlorimuron + Cyprosulfamide, Ethoxysulfuron + Cyprosulfamide, Flazasulfuron + Cyprosulfamide, Florasulam + Cyprosulfamide, Flumetsulam + Cyprosulfamide, Halosulfuron +
Cyprosulfamide, Imazamox + Cyprosulfamide, Imazapic + Cyprosulfamide, Imazapyr + Cyprosulfamide, Imazethapyr + Cyprosulfamide, Mesosulfuron + Cyprosulfamide, Propoxycarbazone + Cyprosulfamide, Sulfosulfuron + Cyprosulfamide, Amidosulfuron + Cyprosulfamide, Chlorsulfuron + Cyprosulfamide, Imazaquin + Cyprosulfamide, Triasulfuron + Cyprosulfamide, Sulfometuron + Cyprosulfamide, Cyclosulfamuron + Cyprosulfamide, Flupyrsulfuron + Cyprosulfamide, Pyrazosulfuron + Cyprosulfamide, Azimsulfuron + Cyprosulfamide, Bensulfuron + Cyprosulfamide, Bispyribac + Cyprosulfamide, Rimsulfuron + Cyprosulfamide, Tritosulfuron + Cyprosulfamide, Sulcotrione + Cyprosulfamide, Clomazone + Cyprosulfamide, Mesotrione + Cyprosulfamide, Topramezone + Cyprosulfamide, Metribuzin + Cyprosulfamide, Bentazon + Cyprosulfamide, Bromoxynil + Cyprosulfamide, Propanil + Cyprosulfamide, Atrazin + Cyprosulfamide, Terbuthylazin + Cyprosulfamide, EPTC + Cyprosulfamide, Tepraloxydim + Cyprosulfamide, Clethodim + Cyprosulfamide, Alloyxdim + Cyprosulfamide, Sethoxydim + Cyprosulfamide, Tralkoxydim + Cyprosulfamide, Clodinafop-propargyl + Cyprosulfamide, Cyhalofop-butyl + Cyprosulfamide, Diclofop-methyl + Cyprosulfamide, Fenoxaprop-P-ethyl + Cyprosulfamide, Fluazifop-P-butyl + Cyprosulfamide, Haloxyfop-methyl + Cyprosulfamide, Haloxyfop-etotyl + Cyprosulfamide, Haloxyfop-R-methyl + Cyprosulfamide, Haloxyfop-ethoxyethyl + Cyprosulfamide, Propaquizafop + Cyprosulfamide, Quizalofop-P-tefuryl + Cyprosulfamide, Quizalofop-P-ethyl + Cyprosulfamide, Acetochlor + Cyprosulfamide, S-Metolachlor + Cyprosulfamide, Flumioxazin + Cyprosulfamide, Flumiclorac + Cyprosulfamide, Fomesafen + Cyprosulfamide, Sulfentrazone + Cyprosulfamide, Dicamba + Cyprosulfamide, MCPA + Cyprosulfamide, MCPB + Cyprosulfamide, 2,4- D + Cyprosulfamide, Clopyralid + Cyprosulfamide, Fluroxypyr + Cyprosulfamide, Picloram + Cyprosulfamide, Triclopyr + Cyprosulfamide, Glufosinate + Cyprosulfamide, Glyphosate + Cyprosulfamide und Pendimethalin + Cyprosulfamide.Cyprosulfamide, Imazamox + Cyprosulfamide, Imazapic + Cyprosulfamide, Imazapyr + Cyprosulfamide, Imazethapyr + Cyprosulfamide, Mesosulfuron + Cyprosulfamide, Propoxycarbazone + Cyprosulfamide, Sulfosulfuron + Cyprosulfamide, Amidosulfuron + Cyprosulfamide, Chlorsulfuron + Cyprosulfamide, Imazaquin + Cyprosulfamide, Triasulfuron + Cyprosulfamide, Sulfometuron + Cyprosulfamide, cyclosulfamuron + cyprosulfamide, flupyrsulfuron + cyprosulfamide, pyrazosulfuron + cyprosulfamide, azimsulfuron + cyprosulfamide, bensulfuron + cyprosulfamide, bispyribac + cyprosulfamide, rimsulfuron + cyprosulfamide, tritosulfuron + cyprosulfamide, sulcotrione + cyprosulfamide, clomazone + cyprosulfamide, mesotrione + cyprosulfamide, topramezone + cyprosulfamide, metribuzin + Cyprosulfamide, Bentazone + Cyprosulfamide, Bromoxynil + Cyprosulfamide, Propanil + Cyprosulfamide, Atrazine + Cyprosulfamide, Terbuthylazine + Cyprosulfamide, EPTC + Cyprosulfamide, Tepraloxydim + Cyprosulfamide, Clethodim + Cyprosulfamide, Alloyxdim + Cyprosulfamide, Sethoxydim + Cyprosulfamide, Tralkoxydim + Cyprosulfamide, Clodinafop-propargyl + Cyprosulfamide, Cyhalofop-butyl + Cyprosulfamide, Diclofop-methyl + Cyprosulfamide, Fenoxaprop-P-ethyl + Cyprosulfamide, Fluazifop-P-butyl + Cyprosulfamides, haloxyfop-methyl + cyprosulfamides, haloxyfop-etotyl + cyprosulfamides, haloxyfop-R-methyl + cyprosulfamides, haloxyfop-ethoxyethyl + cyprosulfamides, propaquizafop + cyprosulfamides, quizalofop-P-tefuryl + cyprosulfamides, quizalofop-P-ethyl + cyprosulfamides, acetochlor + Cyprosulfamide, S-metolachlor + cyprosulfamide, flumioxazine + cyprosulfamide, flumiclorac + cyprosulfamide, fomesafen + cyprosulfamide, sulfentrazone + cyprosulfamide, dicamba + cyprosulfamide, MCPA + cyprosulfamide, MCPB + cyprosulfamide, 2,4-D + cyprosulfamide, clopyralid + cyprosulfamide, fluroxypyr + Cyprosulfamides, Picloram + Cyprosulfamide, Triclopyr + Cyprosulfamide, Glufosinate + Cyprosulfamide, Glyphosate + Cyprosulfamide and Pendimethalin + Cyprosulfamide.
Das Gewichtsverhältnis Safener : Herbizid kann innerhalb weiter Grenzen variieren und liegt vorzugsweise im Bereich von 1 : 100 bis 100 : 1 , insbesondere von 1 : 100 bis 50 : 1 , ganz besonders bevorzugt 1 : 10 bis 10 : 1. Die jeweils optimalen Mengen an Herbizid(en) und Safener(n) sind üblicherweise vom Typ des Herbizids und/oder vom verwendeten Safener sowie von der Art des zu behandelnden Pflanzenbestandes abhängig.The weight ratio safener: herbicide 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, very particularly preferably from 1:10 to 10: 1 Herbicide (s) and safener (s) are usually dependent on the type of herbicide and / or the safener used and on the nature of the plant stock to be treated.
Ganz besonders bevorzugt in den erfindungsgemäßen Pflanzenschutzmittel sind Herbizide aus der Gruppe der ACCase-lnhibitoren, wie Alloxydim, Butroxydim, Clethodim, Clodinafop-propargyl, Cycloxydim, Cyhalofop-butyl, Diclofop-methyl, Fenoxaprop, Fenoxaprop-ethyl, Fenoxaprop-P, Fenoxaprop-P-ethyl, Fluazifop, Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfop-etotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim, Tralkoxydim und Isoxapyrifop; aus der Gruppe der p-Hydroxyphenyl pyruvate dioxygenase (HPPD)-Inhibitoren, wie Benzobicyclon, Benzofenap, Isoxaflutole und dessen Diketonitrile, Mesotrione, Pyrazolynate, Pyrazoxyfen, Sulcotrione und Isoxachlortole; aus der Gruppe der ALS- Inhibitoren, Hydroxybenzonitrile und weiterer verschiedener Wirkstoffgruppen, wie Atrazin, Acetochlor, Aclonifen, Alachlor, Amidochlor, Amidosulfuron, Azimsulfuron, Bentazon, Bensulfuron(-methyl), Bromoxynil(-octanoat/-heptanoat), Butachlor, Bispyribac, Chlorsulfuron, Chlorimuron, Clomazone, Clopyralid, Cinosulfuron, Cyclosulfamuron, 2,4-D-Ester, 2,4-DB-Ester, 2,4-DP-Ester, CMPP-Ester, MCPA- Ester, MCPB, EPTC, Desmedipham, Diflufenican, Dicamba, Ethoxysulfuron, Ethofumesat, Flazasulfuron, Florasulam, Flucarbazone, Flumetsulam, Flufenacet, Fluoroglykofen, Fluroxypyr, Flupyrsulfuron, Foramsulfuron, Flumioxazin, Flumiclorac, Fomesafen, Glufosinate, Glyphosate, Imazapyr, Imazosulfuron, lodosulfuron, lodosulfuron-methyl, loxynil(-octanoat), Lactofen, Halosulfuron, Imazamox, Imazapic, Imazapyr, Imazethapyr, Imazaquin, Metosulam, Mesosulfuron(-methyl), (S- )Metolachlor, Metsulfuron-methyl, Metamitron, Nicosulfuron, Oxyfluorfen, Pendimethalin, Phenmedipham, Picloram, Pinoxaden, Primisulfuron-methyl, Prosulfuron, Propanil, Propoxycarbazone, Pyrazosulfuron(-methyl), Rimsulfuron, Sulfentrazone, Sulfosulfuron, Sulfometuron, Terbuthylazin, Thifensulfuron,Very particularly preferred in the crop protection agents according to the invention are herbicides from the group of ACCase inhibitors, such as alloxydim, butroxydim, clethodim, clodinafop-propargyl, cycloxydim, cyhalofop-butyl, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop- P-ethyl, Fluazifop, Fluazifop-P-butyl, Fluazifop-butyl, Haloxyfop, Haloxyfop-P, Haloxyfopetotyl, Haloxyfop-P-methyl, Metamifop, Profoxydim, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Sethoxydim, Tepraloxydim, Tralkoxydim and Isoxapyrifop; from the group of p-hydroxyphenyl pyruvate dioxygenase (HPPD) inhibitors, such as benzobicyclone, benzofenap, isoxaflutole and its diketonitriles, mesotrione, pyrazolynate, pyrazoxyfen, sulcotrione and isoxachlorotole; from the group of ALS inhibitors, hydroxybenzonitriles and other various active substance groups, such as atrazine, acetochlor, aclonifen, alachlor, amidochlor, amidosulfuron, azimsulfuron, bentazone, bensulfuron (-methyl), bromoxynil (-octanoate / -heptanoate), butachlor, bispyribac, Chlorosulfuron, chlorimuron, clomazone, clopyralid, cinosulfuron, cyclosulfamuron, 2,4-D-esters, 2,4-DB-esters, 2,4-DP-esters, CMPP-esters, MCPA- Esters, MCPB, EPTC, desmedipham, diflufenican, dicamba, ethoxysulfuron, ethofumesate, flazasulfuron, florasulam, flucarbazone, flumetsulam, flufenacet, fluoroglycofen, fluroxypyr, flupyrsulfuron, foramsulfuron, flumioxazine, flumiclorac, fomesafen, glufosinate, glyphosate, imazapyr, imazosulfuron, lodosulfuron, iodosulfuron-methyl, loxynil (-octanoate), lactofen, halosulfuron, imazamox, imazapic, imazapyr, imazethapyr, imazaquin, metosulam, mesosulfuron (-methyl), (S) -metolachlor, metsulfuron-methyl, metamitron, nicosulfuron, oxyfluorfen, pendimethalin, Phenmedipham, picloram, pinoxaden, primisulfuron-methyl, prosulfuron, propanil, propoxycarbazone, pyrazosulfuron (-methyl), rimsulfuron, sulfentrazone, sulfosulfuron, sulfometuron, terbuthylazine, thifensulfuron,
Triasulfuron, Tribenuron, Triclopyr, Triflusulfuron-methyl, Trifluralin, Tritosulfuron, Topramezone, Oxazinon, Oxadiargyl, Metribuzin, und deren Salze, z.B. die Natriumsalze; aus der Gruppe der Pflanzenwuchsregulatoren, wie Ethephon, Cyclanilide und Thidiazuron; aus der Gruppe der Safener, wie AD 67 (4- (dichloroacetyl)-i -oxa-4-azaspiro[4.5]decane), Benoxacor, CL 304,415 (4- carboxymethylchroman-4-carboxylic acid), Cloquintocet, Cloquintocet-mexyl, Cyprosulfamide, Dichlormid, Dicyclonon, DKA-24 (N1 ,N2-diallyl-N2- dichloroacetylglycinamide), Fenchlorazole, Fenchlorazole-ethyl, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen-ethyl, Mefenpyr-diethyl, MG 191 (2- dichloromethyl-2-methyl-1 ,3-dioxolane), Naphthalsäureanhydrid (naphthalene-1 ,8- dicarboxylic anhydride), Oxabetrinil and TI-35 (1-dichloroacetylazepane); sowie Mischungen aus Herbiziden und Safenern, wie Isoxadifen-ethyl-Mischungen mit Foramsulfuron, lodosulfuron-methyl-sodium, Fenoxaprop-P-ethyl, Ethoxysulfuron, wie Mefenpyr-diethyl-Mischungen mit lodosulfuron-methyl-sodium, Mesosulfuron- methyl, Fenoxaprop-P-ethyl, Diclofop-methyl, Sethoxydim, Isoproturon, wie Clodinafop-propargyl + Cloquintocet-mexyl, wie Fenoxaprop-P-ethyl + Fenchlorazole-ethyl, wie Cyprosulfamide-Mischungen mit Flucarbazone, Foramsulfuron, lodosulfuron(-methyl), Metosulam, Metsulfuron(-methyl), Nicosulfuron, Primisulfuron(-methyl), Prosulfuron, Thifensulfuron, Tribenuron, Cloransulam-methyl, Chlorimuron, Ethoxysulfuron, Flazasulfuron, Florasulam, Flumetsulam, Halosulfuron, Imazamox, Imazapic, Imazapyr, Imazethapyr, Mesosulfuron, Propoxycarbazone, Sulfosulfuron, Amidosulfuron, Chlorsulfuron, Imazaquin, Triasulfuron, Sulfometuron, Cyclosulfamuron, Flupyrsulfuron, Pyrazosulfuron, Azimsulfuron, Bensulfuron, Bispyribac, Rimsulfuron, Tritosulfuron, Sulcotrione, Clomazone, Mesotrione, Topramezone, Metribuzin, Bentazon, Bromoxynil, Propanil, Atrazin, Terbuthylazin, EPTC, Tepraloxydim, Clethodim, Alloyxdim, Sethoxydim, Tralkoxydim, Clodinafop-propargyl, Cyhalofop-butyl, Diclofop-methyl, Fenoxaprop-P-ethyl, Fluazifop-P-butyl, Haloxyfop-methyl, Haloxyfop-etotyl, Haloxyfop-R-methyl, Haloxyfop-ethoxyethyl, Propaquizafop, Quizalofop-P-tefuryl, Quizalofop-P-ethyl, Acetochlor, S-Metolachlor, Flumioxazin, Flumiclorac, Fomesafen, Sulfentrazone, Dicamba, MCPA, MCPB, 2,4-D, Clopyralid, Fluroxypyr, Picloram, Triclopyr, Glufosinate, Glyphosate, Pendimethalin.Triasulfuron, tribenuron, triclopyr, triflusulfuron-methyl, trifluralin, tritosulfuron, toramezone, oxazinone, oxadiargyl, metribuzin, and their salts, eg the sodium salts; from the group of plant growth regulators, such as ethephon, cyclanilides and thidiazuron; from the group of safeners, such as AD 67 (4- (dichloroacetyl) -i-oxa-4-azaspiro [4.5] decane), Benoxacor, CL 304,415 (4-carboxymethylchroman-4-carboxylic acid), Cloquintocet, Cloquintocet-mexyl, Cyprosulfamides, dichloromide, dicyclonon, DKA-24 (N1, N2-diallyl-N2-dichloroacetylglycine amides), fenchlorazoles, fenchlorazole-ethyl, fenclorim, flurazoles, fluxofenim, furilazoles, isoxadifen-ethyl, mefenpyr-diethyl, mw 191 (2-dichloromethyl- 2-methyl-1,3-dioxolane), naphthalic anhydride (naphthalenes-1,8-dicarboxylic anhydride), oxabetrinil and TI-35 (1-dichloroacetylazepane); and mixtures of herbicides and safeners, such as isoxadifen-ethyl mixtures with foramsulfuron, iodosulfuron-methyl-sodium, fenoxaprop-P-ethyl, ethoxysulfuron, such as mefenpyr-diethyl mixtures with iodosulfuron-methyl-sodium, mesosulfuron-methyl, Fenoxaprop-P ethyl, diclofop-methyl, sethoxydim, isoproturon, such as clodinafop-propargyl + cloquintocet-mexyl, such as fenoxaprop-P-ethyl + fenchlorazole-ethyl, such as cyprosulfamide mixtures with flucarbazone, foramsulfuron, iodosulfuron (-methyl), metosulam, metsulfuron ( -methyl), nicosulfuron, primisulfuron (-methyl), prosulfuron, thifensulfuron, tribenuron, cloransulam-methyl, chlorimuron, ethoxysulfuron, flazasulfuron, florasulam, flumetsulam, halosulfuron, imazamox, imazapic, imazapyr, imazethapyr, mesosulfuron, propoxycarbazone, sulfosulfuron, amidosulfuron, chlorsulfuron, Imazaquin, triasulfuron, sulfometuron, cyclosulfamuron, flupyrsulfuron, pyrazosulfuron, azimsulfuron, bensulfuron, bispyribac, rimsulfuron, tritosulfuron, sulcotrione, clomazone, mesotrione, toramezone, metribuzin, bentazone, bromoxynil, propanil, atrazine, terbuthylazine, EPTC, tepraloxydim, clethodim, alloyxdim, Sethoxydim, tralkoxydim, clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, fenoxaprop-P-ethyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-etotyl, haloxyfop-R-methyl, haloxyfop-ethoxyethyl, propaquizafop, quizalofop P-tefuryl, quizalofop-P-ethyl, acetochlor, S-metolachlor, flumioxazine, flumiclorac, fomesafen, sulfentrazone, dicamba, MCPA, MCPB, 2,4-D, clopyralid, fluroxypyr, picloram, triclopyr, glufosinate, glyphosate, pendimethalin.
Die bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittel enthalten in der Regel 0,01 bis 99 Gew.-%, insbesondere 0,1 bis 95 Gew.-%, der Wirkstoffe aus der Gruppe der Herbizide und/oder Safener. Die flächenbezogenen Aufwandmengen der Komponente (A) liegen im allgemeinen zwischen 10 und 2000 g AS/ha (AS = Aktivsubstanz, d. h. Aufwandmenge bezogen auf den aktiven Wirkstoff), bevorzugt zwischen 50 und 300 g AS/ha.The crop protection agents used in the process according to the invention generally contain from 0.01 to 99% by weight, in particular from 0.1 to 95% by weight, of the active compounds from the group of herbicides and / or safeners. The surface-related application rates of component (A) are generally between 10 and 2000 g AS / ha (AS = active substance, that is, application rate based on the active ingredient), preferably between 50 and 300 g AS / ha.
Tributoxyethylphosphat (TBEP) als Komponente (B) hat die CAS Regno: 78-51-3 und wird unter diesem Eintrag in der Fachliteratur in seinen weiteren Eigenschaften ausführlich beschrieben.Tributoxyethyl phosphate (TBEP) as component (B) has the CAS Regno: 78-51-3 and is described in detail in this entry in the literature in its other properties.
Der Gehalt an TBEP (B) in den bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmitteln ist abhängig von der flächenbezogenen Applikationsmenge pro Hektar (ha) und muss daher entsprechend angepasst werden. Dies gilt auch für die Herstellung einer Applikationslösung, beispielsweise einer Spritzbrühe, beim Einsatz des erfindungsgemäßen Verfahrens. Die flächenbezogenen Applikationsmengen für TBEP (B) liegen zwischen 2,5 und 150 g/ha, bevorzugt 5 bis 100 g/ha, besonders bevorzugt 10 bis 100 g/ha, wobei das Volumen der Spritzbrühe in der Regel zwischen 100-500 L/ha liegt.The content of TBEP (B) in the pesticides used in the method according to the invention is dependent on the area-related application amount per hectare (ha) and must therefore be adjusted accordingly. This also applies to the preparation of an application solution, for example a spray mixture, when using the method according to the invention. The area-related application rates for TBEP (B) are between 2.5 and 150 g / ha, preferably 5 to 100 g / ha, more preferably 10 to 100 g / ha, the volume of the spray mixture generally being between 100-500 L / ha lies.
Gegebenenfalls kann als Komponente (C) bei der Herstellung von Pflanzenschutzmitteln für das erfindungsgemäße Verfahren und/oder der Applikation gemäß des erfindungsgemäßen Verfahrens, bevorzugt in Form von Spritzbrühen, die Zugabe eines oder mehrerer Emulgatoren notwendig sein. Geeignete Emulgatoren sind aus der Gruppe der ionischen und nicht-ionischen Emulgatoren und deren Gemische mit HLB-Werten von 10 bis 17 (z.B. Emulgator 1371B). Sie können entweder direkt und/oder durch die Formulierung der Komponenten (A) und/oder (B) zugesetzt werden.Optionally, as component (C) in the preparation of Pesticides for the method according to the invention and / or the application according to the inventive method, preferably in the form of spray mixtures, the addition of one or more emulsifiers may be necessary. Suitable emulsifiers are from the group of ionic and nonionic emulsifiers and mixtures thereof with HLB values of 10 to 17 (eg emulsifier 1371B). They may be added either directly and / or by the formulation of components (A) and / or (B).
Die flächen bezogenen Aufwandmengen der Komponente (C) liegen bei der Applikation des erfindungsgemäßen Pflanzenschutzmittels und/oder des erfindungsgemäßen Verfahrens im allgemeinen zwischen 10 und 200 g/ha, bevorzugt zwischen 20 und 200 g/ha.The surface-related application rates of component (C) are in the application of the plant protection agent according to the invention and / or the method according to the invention generally between 10 and 200 g / ha, preferably between 20 and 200 g / ha.
Als weitere Hilfs - und Zusatzstoffe (Komponente D)1 die in den, gemäß dem erfindungsgemäßen Verfahren, vorzugsweise flüssige Formulierungen enthalten sein können, kommen alle üblichen Formulierhilfsmittel in Frage, wie organische Solventien, Entschäumer, von Komponente (C) verschiedene Emulgatoren, Dispergiermittel, Konservierungsmittel, Säuren und Basen, Farbstoffe, Füllstoffe und auch Wasser.As further auxiliaries and additives (component D) 1 which may be present in the formulations according to the invention, preferably liquid formulations, all customary formulation auxiliaries are suitable, such as organic solvents, defoamers, emulsifiers other than component (C), dispersants, Preservatives, acids and bases, dyes, fillers and also water.
Als organische Solventien kommen alle üblichen organischen Lösungsmittel in Betracht, welche die eingesetzten agrochemischen Wirkstoffe gut lösen. Vorzugsweise genannt seien aliphatische und aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie Toluol, XyIoI, Solvesso®, Pflanzen- und Mineralöle, wie Testbenzin, Petroleum, Alkylbenzole und Spindelöl, weiterhin Propylencarbonat, Tetrachlormethan, Chloroform, Methylenchlorid und Dichlormethan, außerdem Ester, wie Ethylacetat, Lactate femer Lactone, wie Butyrolacton, außerdem Lactame, wie N-Methylpyrrolidon, N-Octylpyrrolidon, N- Dodecylpyrrolidon N-Octylcaprolactam und N-Methylcaprolactam, γ-Butyrolacton, Dimethylformamid sowie Tributylphosphat.Suitable organic solvents are all customary organic solvents which readily dissolve the agrochemical active ingredients used. Aliphatic and aromatic, optionally halogenated hydrocarbons, such as toluene, xylene, Solvesso ®, vegetable and mineral oils, such as white spirit, kerosene, alkylbenzenes and spindle oil, furthermore propylene carbonate, carbon tetrachloride, chloroform, methylene chloride and methylene chloride, and also esters, such as ethyl acetate, Lactates furthermore lactones, such as butyrolactone, as well as lactams, such as N-methylpyrrolidone, N-octylpyrrolidone, N-dodecylpyrrolidone N-octylcaprolactam and N-methylcaprolactam, γ-butyrolactone, dimethylformamide and tributyl phosphate.
Als Entschäumer kommen übliche, in Formulierungen von agrochemischen Wirkstoffen vorhandene Entschäumer in Frage. Beispielhaft genannt seien Silikonöle, Dispersionen von Silikonölen, Magnesiumstearat, Phosphin- und Phosphonsäuren, insbesondere Fluowet PL 80®.As defoamers are common, in formulations of agrochemical Active substances existing defoamers in question. Examples include silicone oils, dispersions of silicone oils, magnesium stearate, phosphinic and phosphonic acids, in particular Fluowet PL 80 ® .
Als von Komponente (C) verschiedene Emulgatoren kommen übliche, inAs of component (C) different emulsifiers are common, in
Formulierungen von agrochemischen Wirkstoffen vorhandene oberflächenative Substanzen in Frage. Beispielhaft genannt seien ethoxylierte Nonylphenole, Polyethylenglykolether von linearen Alkoholen, Endgruppen-verschlossene und nicht Endgruppen-verschlossene alkoxylierte lineare und verzweigte, gesättigte und ungesättigte Alkohole, Umsetzungsprodukte von Alkylphenolen mit Ethylenoxid und/oder Propylenoxid, Ethylenoxid- Propylenoxid-Blockcopolymere, Polyethylenglykole und Polypropylenglykole, weiterhin Fettsäureester, Endgruppen- verschlossene und nicht Endgruppen-verschlossene alkoxylierte lineare und verzweigte, gesättigte und ungesättigte Fettsäuren, Alkylsulfonate, Alkylsulfate, Alkylethersulfate, Arylsulfate, ethoxylierte Arylalkylphenole, wie zum BeispielFormulations of agrochemical agents existing surface-active substances in question. Examples which may be mentioned are ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, end-capped and non-end-capped alkoxylated linear and branched, saturated and unsaturated alcohols, reaction products of alkylphenols with ethylene oxide and / or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols Fatty acid esters, end capped and non end capped alkoxylated linear and branched, saturated and unsaturated fatty acids, alkyl sulfonates, alkyl sulfates, alkyl ether sulfates, aryl sulfates, ethoxylated arylalkylphenols such as
Tristyryl-phenol-ethoxylat mit durchschnittlich 16 Ethylenoxid-Einheiten pro Molekül, weiterhin ethoxylierte und propoxylierte Arylalkylphenole sowie sulfatierte oder phosphatierte Arylalkylphenol-ethoxylate bzw. -ethoxy- und -propoxylate.Tristyrylphenol ethoxylate having an average of 16 ethylene oxide units per molecule, further ethoxylated and propoxylated arylalkylphenols and sulfated or phosphated arylalkylphenol ethoxylates or ethoxy and propoxylates.
Als Dispergiermittel kommen alle üblicherweise in Pflanzenschutzmitteln für diesen Zweck eingesetzten Substanzen in Betracht. Vorzugsweise genannt seien, neben den oben unter von Komponente (C) verschiedenen Emulgatoren genannten Verbindungen, natürliche und synthetische, wasserlösliche Polymere, wie Gelatine, Stärke und Cellulosederivate, insbesondere Celluloseester und Celluloseether, femer Polyvinylalkohol, Polyvinylpyrrolidon, Polyacrylsäure, Ligninsulfonate, Polymethacrylsäure und Co-Polymerisate aus (Meth)acrylsäure und (Meth)acrylsäureestern, und außerdem auch mit Alkalimetallhydroxid neutralisierte Co-Polymerisate aus Methacrylsäure und Methacrylsäureester.Suitable dispersants are all substances customarily used in crop protection agents for this purpose. In addition to the compounds mentioned above under component (C) different emulsifiers, preference is given to natural and synthetic water-soluble polymers, such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, furthermore polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, ligninsulfonates, polymethacrylic acid and co-polymers. Polymers of (meth) acrylic acid and (meth) acrylic acid esters, and also neutralized with alkali metal hydroxide co-polymers of methacrylic acid and methacrylic acid ester.
Als Konservierungsmittel kommen alle üblicherweise für diesen Zweck inAs preservatives, all are commonly used for this purpose
Pflanzenbehandlungsmitteln vorhandenen Substanzen in Betracht. Als Beispiele genannt seien Preventol® und Proxel®. Als Farbstoffe kommen alle für die Herstellung von Pflanzenschutzmitteln üblichen anorganischen oder organischen Farbstoffe in Frage. Beispielhaft genannt seien Titandioxid, Farbruß, Zinkoxid und Blaupigmente.Plant treatment agents existing substances into consideration. Be mentioned as examples Preventol® ® and Proxel ®. Suitable dyes are all customary for the production of pesticides inorganic or organic dyes. Examples include titanium dioxide, carbon black, zinc oxide and blue pigments.
Als Füllstoffe kommen alle üblicherweise für diesen Zweck in Pflanzenschutzmitteln eingesetzten Substanzen in Betracht. Vorzugsweise genannt seien anorganische Partikel, wie Carbonate, Silikate und Oxide mit einer mittleren Teilchengröße von 0,005 bis 10 μm, besonders bevorzugt von 0,02 bis 2 μm. Beispielhaft erwähnt seien Siliziumdioxid, sogenannte hochdisperse Kieselsäure, Kieselgele, sowie natürliche und synthetische Silikate und Alumosilikate.Suitable fillers are all substances normally used for this purpose in crop protection agents. Preferably mentioned are inorganic particles, such as carbonates, silicates and oxides having an average particle size of 0.005 to 10 .mu.m, more preferably from 0.02 to 2 microns. Examples include silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates.
Als Verbindungen, die als Emulsions-Stabilisatoren und/oder Kristallisationsinhibitoren wirken, kommen alle üblicherweise für diesen Zweck in Pflanzenschutzmitteln eingesetzte Substanzen in Betracht.Suitable compounds which act as emulsion stabilizers and / or crystallization inhibitors are all substances conventionally used for this purpose in crop protection agents.
Der Gehalt an den einzelnen Komponenten in den bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmitteln und die flächenbezogenen Applikationsmenge beim Einsatz des erfindungsgemäßen Verfahrens kann innerhalb eines größeren Bereichs variiert werden.The content of the individual components in the crop protection agents used in the method according to the invention and the area-related application amount when using the method according to the invention can be varied within a substantial range.
Zu den für die bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmitteln mit den Komponenten (A) und (B) sowie gegebenenfalls den Komponenten (C) und/oder (D) in Frage kommenden Formulierungstypen gehören prinzipiell alle Formulierungen, die auf Pflanzen oder deren Vermehrungsgut ausgebracht werden. Die zu deren Herstellung verwendeten Verfahren sind dem Fachmann allgemein geläufig und beispielsweise beschrieben in Winnacker-Küchler, „Chemische Technologie" Band 7, C. Hanser Verlag München, 4. Aufl., 1986; J.W. van Valkenburg, „Pesticide Formulations", Marcel Dekker N.Y., 1973, K. Martens, „Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd., London, oder Mollet, Grubenmann, „Formulierungstechnik", Wiley-VCH-Verlag, Weinheim, 2000. Daneben kommen für die einzelnen Komponenten des erfindungsgemäßen Verfahrens prinzipiell auch alle Formulierungstypen in Frage.In principle, all formulations which are applied to plants or their propagation material belong to the types of formulation which may be used for the crop protection agents used in the process according to the invention with components (A) and (B) and optionally components (C) and / or (D) , The processes used for their preparation are generally known to the person skilled in the art and are described, for example, in Winnacker-Kuchler, "Chemische Technologie" Volume 7, C. Hanser Verlag Munich, 4th ed., 1986, JW van Valkenburg, "Pesticide Formulations", Marcel Dekker NY, 1973, K. Martens, "Spray Drying Handbook", 3rd ed., 1979, G. Goodwin Ltd., London, or Mollet, Grubenmann, "Formulation Technology", Wiley-VCH-Verlag, Weinheim, 2000. In addition, for the individual components of the method according to the invention in principle all formulation types in question.
Beispiele für Formulierungstypen sind die im „Manual on development and use of FAO and WHO specifications for pesticides" (FAO and WHO, 2002, appendix E) erwähnten (jeweils Verwendung der GCPF-Formulierungskodes mit englischer Abkürzung und Bezeichnung): AL Any other liquid; AP Any other powder; CF Capsule Suspension for Seed Treatment; CG Encapsulated granule; CL Contact liquid or gel; CP Contact powder; CS Capsule Suspension; DC Dispersible concentrate; DP Dustable powder; DS Powder fbr dry seed treatment; ECExamples of formulation types are those mentioned in the "Manual on development and use of FAO and WHO specifications for pesticides" (FAO and WHO, 2002, appendix E) (each using the GCPF formulation codes with English abbreviation and designation): AL Any other liquid; AP Capsule Suspension; DC Powder Fbr dry seed treatment; EC Capsule Suspension; DC Dispersible concentrate; DC Powder;
Emulsifiable concentrate; ED Electrochargeable liquid; EG Emulsifiable Granule; EO Emulsion, water in oil; EP emulsifiable powder; ES Emulsion for seed treatment; EW Emulsion, oil in water; FG Fine granule; FS Flowable concentrate for seed treatment; GF Gel for Seed Treatment; GG Macrogranule; GL Emulsifiable gel; GP Flo-dust; GR Granule; GS Grease; GW Water soluble gel; HN Hot fogging concentrate; KK Combi-pack solid/liquid; KL Combi-pack liquid/liquid; KN CoId fogging concentrate; KP Combi-pack solid/solid; LA Lacquer; LS Solution for seed treatment; ME Microemulsion; MG Microgranule; OD OiI dispersiσn; OF OiI miscible flowable concentrate/oil miscible Suspension; OL OiI miscible liquid; OP OiI dispersible powder; PA Paste; PC Gel or paste concentrate; PO Pour-on; PR Plant rodlet; PT Pellet; SA Spot-on; SC Suspension concentrate; SD Suspension concentrate for direct application; SE Suspo-emulsion; SG Water soluble granule; SL Soluble concentrate; SO Spreading oil; SP Water soluble powder; SS Water soluble powder for seed treatment; ST Water soluble tablet; SU Ultra-low volume (ULV) Suspension; TB Tablet; TC Technical material; TK Technical concentrate; UL Ultra-low volume (ULV) liquid; WG Water dispersible granules; WP Wettable powder; WS Water dispersible powder for slurry seed treatment; WT Water dispersible tablet; XX Others.Emulsifiable concentrate; ED Electrochargeable liquid; EC Emulsifiable Granules; EO emulsion, water in oil; EP emulsifiable powder; ES Emulsion for seed treatment; EW emulsion, oil in water; FG fine granule; FS Flowable concentrate for seed treatment; GF Gel for Seed Treatment; GG Macrogranule; GL emulsifiable gel; GP flo-dust; GR Granule; GS Grease; GW Water soluble gel; HN Hot fogging concentrate; KK Combi-pack solid / liquid; KL Combi-pack liquid / liquid; KN CoId fogging concentrate; KP Combi-pack solid / solid; LA Lacquer; LS Solution for seed treatment; ME microemulsion; MG microgranules; OD OiI dispersiσn; Oxygen miscible flowable concentrate / oil miscible suspension; OL OiI miscible liquid; OP OiI dispersible powder; PA paste; PC gel or paste concentrate; PO Pour-on; PR Plant rodlet; PT pellet; SA spot-on; SC suspension concentrate; SD suspension concentrate for direct application; SE suspo-emulsion; SG Water Soluble Granule; SL Soluble concentrate; SO Spreading oil; SP Water soluble powder; SS Water soluble powder for seed treatment; ST Water soluble tablet; SU ultra-low volume (ULV) suspension; TB tablet; TC Technical material; TK Technical concentrate; UL Ultra-low volume (ULV) liquid; WG Water dispersible granules; WP Wettable powder; WS Water dispersible powder for slurry seed treatment; WT Water dispersible tablet; XX Others.
Bevorzugt sind flüssige Formulierungstypen. Hierzu gehören die Formulierungstypen OD OiI dispersion; DC (GCPF-Formulierungskode für dispergierbares Konzentrat); EC (GCPF-Formulierungskode für Emulsionskonzentrat); EW (GCPF- Formulierungskode für ÖI-in-Wasser-Emulsion); ES (GCPF-Formulierungskode für Emulsionsbeize); FS (GCPF-Formulierungskode für Mehrphasenkonzentrat zur Saatgutbehandlung); EO (GCPF-Formulierungskode für Wasser in Öl Emulsion); ME (GCPF-Formulierungskode für Mikroemulsion); SE (GCPF-Formulierungskode für Suspoemulsion); SL (GCPF-Formulierungskode für wasserlösliches Konzentrat); CS (GCPF-Formulierungskode für Kapselsuspension) und AL (GCPF- Formulierungskode für gebrauchsfertige Flüssigformulierung, sonstige Flüssigkeiten zur unverdünnten Anwendung).Preference is given to liquid formulation types. These include the formulation types OD OiI dispersion; DC (dispersible concentrate GCPF formulation code); EC (GCPF Formulation Code for Emulsion Concentrate); EW (GCPF Formulation code for oil-in-water emulsion); ES (GCPF Formulation Code for Emulsion Stain); FS (GCPF Formulation Code for Multiphase Concentrate for Seed Treatment); EO (GCPF formulation code for water in oil emulsion); ME (GCPF Formulation Code for Microemulsion); SE (GCPF formulation code for suspoemulsion); SL (GCPF formulation code for water-soluble concentrate); CS (Capsule Suspension GCPF Formulation Code) and AL (GCPF Formulation Code for ready-to-use liquid formulation, other liquids for undiluted use).
Besonders bevorzugt sind Öldispersionen (syn. oil dispersion; Formulierungstyp OD) Emulsionskonzentrate (Formulierungstyp EC).Especially preferred are oil dispersions (syn. Oil dispersion, formulation type OD), emulsion concentrates (formulation type EC).
In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 90 Gew.-%; der Rest zu 100 Gew.-% besteht aus TBEP (B) und üblichen Formulierungsbestandteilen (Emulgator, Hilfs- und Zusatzstoffen), welches für alle Formulierungen gilt. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0.05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt.und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%. Bei Öldispersionen kann die Wirkstoffkonzentration etwa 1 bis 50, vorzugsweise 3 bis 30 Gew.-% betragen.In wettable powders, the active ingredient concentration z. B. about 10 to 90 wt .-%; the remainder to 100% by weight consists of TBEP (B) and customary formulation constituents (emulsifier, auxiliaries and additives), which applies to all formulations. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In the case of oil dispersions, the concentration of active ingredient may be about 1 to 50, preferably 3 to 30,% by weight.
Weiterhin Gegenstand der Erfindung ist ein Verfahren zur Bekämpfung von Schadorganismen, vorzugsweise schädlichen Pflanzen, wobei die im erfindungsgemäßen Verfahren eingesetzten Komponenten, bevorzugt in einer wirksamen Menge, auf die Schadpflanzen appliziert wird. Die Erfindung betrifft weiterhin auch erfindungsgemäße Verfahren, enthaltend mindestens die Komponenten (A) und (B), die in einer bevorzugten Ausführungsform überadditive Effekte (Synergismus) zeigen. Aufgrund der verbesserten Kontrolle der Schadorganismen durch die erfindungsgemäßen Verfahren wird es möglich, die Aufwandmenge zu senken und/oder die Sicherheitsmarge zu erhöhen. Beides ist sowohl ökonomisch als auch ökologisch sinnvoll. Die Wahl der von den Komponenten (A) und (B) einzusetzenden Mengen und das Verhältnis der Komponenten (A) : (B) sind dabei von einer ganzen Reihe von Faktoren abhängig.The invention further relates to a method for controlling harmful organisms, preferably harmful plants, wherein the components used in the process according to the invention, preferably in an effective amount, is applied to the harmful plants. The invention further relates to processes according to the invention containing at least the components (A) and (B), which in a preferred embodiment show superadditive effects (synergism). Due to the improved control of harmful organisms by the method according to the invention, it is possible to reduce the application rate and / or to increase the safety margin. Both are economically as well as ecologically sensible. The choice of the amounts to be used by components (A) and (B) and the ratio of components (A): (B) are dependent on a whole series of factors.
Die Herstellung der bei den erfindungsgemäßen Verfahren verwendetenThe preparation of the used in the inventive method
Pflanzenschutzmittel erfolgt z.B. in der Weise, dass man die Komponenten in den jeweils gewünschten Verhältnissen miteinander vermischt. Handelt es sich bei den Herbiziden und/oder Safenern, im Folgenden als agrochemische Wirkstoffe bezeichnet, um eine Festsubstanz, so setzt man diesen im allgemeinen entweder in fein gemahlener Form oder in Form einer Lösung oder Suspension in einem organischen Solvens oder Wasser ein. Ist der agrochemische Wirkstoff flüssig, so erübrigt sich häufig die Verwendung eines organischen Lösungsmittels. Es ist außerdem möglich, einen festen agrochemischen Wirkstoff in Form einer Schmelze einzusetzen.Plant protection agent is e.g. in such a way that the components are mixed together in the desired ratios. If the herbicides and / or safeners, hereinafter referred to as agrochemical active ingredients, are solids, they are generally used either in finely ground form or in the form of a solution or suspension in an organic solvent or water. If the agrochemical active ingredient is liquid, the use of an organic solvent is often unnecessary. It is also possible to use a solid agrochemical active ingredient in the form of a melt.
Die Temperaturen können bei der Durchführung des Verfahrens in einem bestimmten Bereich variiert werden. Man arbeitet im allgemeinen bei Temperaturen zwischen 00C und 800C, vorzugsweise zwischen 100C und 600C.The temperatures can be varied within a certain range when carrying out the process. It generally works at temperatures between 0 0 C and 80 0 C, preferably between 10 0 C and 60 0 C.
Zur Herstellung der bei den erfindungsgemäßen Verfahren verwendetenFor the preparation of the used in the inventive method
Pflanzenschutzmittel geht man im Allgemeinen so vor, dass man TBEP (B) mit einem oder mehreren der agrochemischen Wirkstoffe (A) sowie gegebenenfalls mit dem Emulgator (C) und den Hilfs- und Zusatzstoffen (D) vermischt. Die Reihenfolge, in der die Komponenten miteinander vermischt werden, hängt vom jeweiligen Formulierungstyp ab.Plant protection agents are generally used by mixing TBEP (B) with one or more of the agrochemical active ingredients (A) and optionally with the emulsifier (C) and the auxiliary substances and additives (D). The order in which the components are mixed together depends on the type of formulation.
Zur Durchführung des Herstellungsverfahrens kommen übliche Geräte in Betracht, die zur Herstellung von agrochemischen Formulierungen eingesetzt werden.For the implementation of the manufacturing process customary devices are considered, which are used for the production of agrochemical formulations.
Zum Einsatz des bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittels und zur Durchführung des erfindungsgemäßen Verfahrens können als Applikationsformen alle, dem Fachmann als gebräuchlich bekannten Verfahren verwendet werden; beispielsweise genannt seien: Spritzen, Tauchen, Nebeln sowie eine Reihe spezieller Verfahren zur direkten unter- oder oberirdischen Behandlung von gesamten Pflanzen oder Teilen (Saatgut, Wurzel, Stolonen, Stengel, Stamm, Blatt), wie beispielsweise Stamminjektion bei Bäumen oder Stengelbandagen bei perennierenden Pflanzen, und eine Reihe spezieller indirekter Applikationsverfahren.For use of the crop protection agent used in the process according to the invention and for carrying out the process according to the invention, all forms of administration known to those skilled in the art may be used as application forms; Examples include: spraying, dipping, misting and a number of special processes for direct under- or above-ground treatment of whole plants or parts (seed, root, stolons, stems, stem, leaf), such as stem injection in trees or stem bandages in perennials , and a number of special indirect application methods.
Die jeweilige flächen- und/oder objektbezogene Aufwandmenge der bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittel unterschiedlichster Formulierungstypen und des erfindungsgemäßen Verfahrens zur Bekämpfung der genannten Schadorganismen variiert sehr stark. Im Allgemeinen werden hierfür die, dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannten Applikationsmedien in den gebräuchlichen Mengen eingesetzt; wie beispielsweise von mehreren hundert Liter Wasser pro Hektar bei Standard- Spritzverfahren über wenige Liter Öl pro Hektar bei der .Ultra Low Volume'-The respective surface and / or object-related application rate of the crop protection agents of the most varied types of formulations used in the process according to the invention and of the process according to the invention for controlling said harmful organisms varies greatly. In general, the application media known to those skilled in the art as customary for the respective field of application are generally used in the customary amounts; for example, from several hundred liters of water per hectare in standard spraying over a few liters of oil per hectare in the "Ultra Low Volume"
Flugzeugapplikation bis hin zu wenigen Millilitern einer physiologischen Lösungen bei Injektionsverfahren. Die Konzentrationen der bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittel in den entsprechenden Applikationsmedien variieren daher in einem weiten Bereich und sind vom jeweiligen Einsatzgebiet abhängig. Im Allgemeinen werden Konzentrationen verwendet, die dem Fachmann als gebräuchlich für das jeweilige Einsatzgebiet bekannt sind. Bevorzugt sind Konzentrationen von 0,01 Gew.-% bis 99 Gew.-%, besonders bevorzugt von 0,1 Gew.-% bis 90 Gew.-%.Aircraft application down to a few milliliters of physiological solutions in injection procedures. The concentrations of the crop protection agents used in the process according to the invention in the corresponding application media therefore vary widely and depend on the respective field of use. In general, concentrations are used which are known to the person skilled in the art as customary for the respective field of use. Preference is given to concentrations of from 0.01% by weight to 99% by weight, particularly preferably from 0.1% by weight to 90% by weight.
Die bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittel unterschiedlichster Formulierungstypen, wie auch die zur Durchführung des erfindungsgemäßen Verfahrens notwendigen Komponenten, können z.B. in den für Flüssigpräparate üblichen Zubereitungsformen entweder als solche oder nach vorherigem Verdünnen mit Wasser ausgebracht werden, also z.B. als Emulsionen, Suspensionen oder Lösungen. Die Anwendung erfolgt dabei nach üblichen Methoden, also z.B. durch Verspritzen, Gießen oder Injizieren.The pesticides used in the process according to the invention of the most varied formulation types, as well as the components necessary for carrying out the process according to the invention, can be found, for example, in US Pat Liquid preparations usual preparation forms either as such or after prior dilution with water are applied, so for example as emulsions, suspensions or solutions. The application is carried out by conventional methods, eg by spraying, pouring or injecting.
Die Aufwandmenge an den bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmitteln unterschiedlichster Formulierungstypen, wie auch die zur Durchführung des erfindungsgemäßen Verfahrens notwendigen Komponenten, kann innerhalb eines größeren Bereiches variiert werden. Sie richtet sich nach den jeweiligen Herbiziden und/oder Safenern und nach deren Gehalt in den Formulierungen.The application rate of the crop protection agents of the most varied formulation types used in the process according to the invention, as well as the components necessary for carrying out the process according to the invention, can be varied within a relatively wide range. It depends on the particular herbicides and / or safeners and their content in the formulations.
Bei dem erfindungsgemäßen Verfahren zur Förderung der Penetration von Wirkstoffen in Pflanzen wird das zu verwendende TBEP (B) in der Regel zusammen mit dem bzw. den Wirkstoffen (A) oder unmittelbar hintereinander ausgebracht, vorzugsweise in Form einer Spritzbrühe, welche TBEP (B) in erfindungsgemäßen Mengen und den oder die Wirkstoffe (A) in wirksamen Mengen und gegebenenfalls einen oder mehrere Emulgatoren (C) enthält. Zusätzlich können weitere übliche Hilfs- und Zusatzmittel zugesetzt werden. Die Spritzbrühe wird bevorzugt auf Basis von Wasser und/oder einem Öl, z.B. einem hochsiedenden Kohlenwasserstoff wie Kerosin oder Paraffin hergestellt. Dabei können die Komponenten für das erfindungsgemäße Verfahren entweder als Tankmischung oder über eine „Fertig- Formulierung" ("ready-to-use formulation"; Co-Formulierung) realisiert werden.In the method according to the invention for promoting the penetration of active substances into plants, the TBEP (B) to be used is generally applied together with the active substance (A) or directly after one another, preferably in the form of a spray mixture containing TBEP (B) in inventive amounts and the active ingredient (s) in effective amounts and optionally one or more emulsifiers (C). In addition, other customary auxiliaries and additives can be added. The spray mixture is preferably based on water and / or an oil, e.g. made of a high boiling hydrocarbon such as kerosene or paraffin. The components for the process according to the invention can be realized either as a tank mixture or via a "ready-to-use formulation" (co-formulation).
Im Falle von Herbiziden und/oder Safenern ist das Aufbringen auf die Schadpflanze bzw. Kulturpflanze bevorzugt. Die erfindungsgemäß behandelten Pflanzen sind, soweit es den Einsatz von Herbiziden betrifft, alle Arten von Schadpflanzen, wie Unkräutern. Im Hinblick auf die Kulturpflanzen ist die Anwendung in wirtschaftlich bedeutenden, beispielsweise auch transgenen Kulturen von Nutz- und Zierpflanzen, z.B. von Getreide, wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais, oder auch Kulturen von Erdnuss, Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten bevorzugt. Die bei den erfindungsgemäßen Verfahren verwendeten Pflanzenschutzmittel, sowie die erfindungsgemäßen Verfahren, weisen eine Reihe von Vorteilen auf. So wird die allgemeine Penetration der Wirkstoffe in das Pflanzengewebe durch TBEP deutlich verbessert. Das schnellere Einsetzen der Penetration bewirkt somit auch eine höhere Regenfestigkeit. Gleichzeitig ist die Penetration bei niedrigeren Temperaturen (beispielsweise kleiner 15° C) verbessert. Im Hinblick auf die Kulturpflanzenverträglichkeit erwies sich in Versuchen TBEP als verträglicher als andere Alkylester-Additive. Insgesamt ermöglicht die Verwendung von TBEP damit Einsparungen an den eingesetzten Wirkstoffen. Daneben ist TBEP weniger belastend für die Umwelt, da es über eine reduzierte Flüchtigkeit verfügt.In the case of herbicides and / or safeners, application to the harmful plant or crop is preferred. As far as the use of herbicides is concerned, the plants treated according to the invention are all types of harmful plants, such as weeds. With regard to the crop plants, the application in economically important, for example, transgenic crops of useful and ornamental plants, such as cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or even cultures of peanut, sugar beet , Cotton, soy, rapeseed, potato, tomato, pea and other vegetables are preferred. The crop protection agents used in the process according to the invention, as well as the processes according to the invention, have a number of advantages. Thus, the general penetration of the active ingredients into the plant tissue by TBEP is significantly improved. The faster onset of penetration thus also causes a higher rainfastness. At the same time, the penetration is improved at lower temperatures (for example less than 15 ° C.). In terms of crop plant compatibility, TBEP has been found to be more compatible than other alkyl ester additives in trials. Overall, the use of TBEP thus allows savings on the active ingredients used. In addition, TBEP is less harmful to the environment as it has a reduced volatility.
Die Erfindung wird durch die Beispiele näher erläutert ohne sie darauf zu beschränken.The invention is further illustrated by the examples without being limited thereto.
BeispieleExamples
Penetrationstestpenetration test
In diesem Test wurde die Penetration von Wirkstoffen durch enzymatisch isolierte Kutikeln von Apfelbaumblättern gemessen. Die Kutikeln repräsentieren alle grünen Pflanzenteile, wie Blattspreite, Blattstiel, Stengel, Stamm, Hypokotyl und viele Früchte.In this test, the penetration of drugs was measured by enzymatically isolated cuticle of apple tree leaves. The cuticles represent all green parts of plants, such as leaf blade, petiole, stalk, stem, Hypocotyl and many fruits.
Verwendet wurden Blätter, die in voll entwickeltem Zustand von Apfelbäumen der Sorte Golden Delicious abgeschnitten wurden. Die Isolierung der Kutikeln erfolgte in der Weise, dassSheets were used, which were cut in the fully developed state of apple trees of the variety Golden Delicious. The isolation of the cuticles took place in such a way that
zunächst auf der Unterseite mit Farbstoff markierte und ausgestanzte Blattscheiben mittels Vakuuminfiltration mit einer auf einen pH-Wert zwischen 3 und 4 gepufferten Pectinase-Lösung (0,2 bis 2 Gew.-%ig) gefüllt wurden, dann Natriumazid hinzugefügt wurde undinitially on the underside with dye-marked and punched leaf discs were filled by means of vacuum infiltration with a buffered to a pH between 3 and 4 pectinase solution (0.2 to 2 wt .-%), then sodium azide was added and
die so behandelten Blattscheiben bis zur Auflösung der ursprünglichen Blattstruktur und zur Ablösung der nicht zellulären Kutikula stehen gelassen wurden.the treated leaf discs were allowed to stand until the original leaf structure had dissolved and the non-cellular cuticle detached.
Danach wurden nur die von Spaltöffnungen und Haaren freien Kutikeln der Blattoberseiten weiter verwendet. Sie wurden mehrfach abwechselnd mit Wasser und einer Pufferlösung vom pH-Wert 7 gewaschen. Die erhaltenen sauberen Kutikel wurden schließlich auf Teflonplättchen aufgezogen und mit einem schwachen Luftstrahl geglättet und getrocknet.Thereafter, only the cuticle openings and hair-free cuticle of the leaf tops were used. They were washed several times alternately with water and a pH 7 buffer solution. The resulting clean cuticles were finally grown on Teflon flakes and smoothed with a gentle jet of air and dried.
Im nächsten Schritt wurden die so gewonnenen Kutikelmembranen für Membran- Transport-Untersuchungen in Diffusionszellen (= Transportkammern) aus Edelstahl eingelegt. Dazu wurden die Kutikeln mit einer Pinzette mittig auf die mit Silikonfett bestrichenen Ränder der Diffusionszellen platziert und mit einem ebenfalls gefetteten Ring verschlossen. Die Anordnung wurde so gewählt, dass die morphologische Außenseite der Kutikeln nach außen, also zur Luft, gerichtet war, während die ursprüngliche Innenseite dem Inneren der Diffusionszelle zugewandt war. Die Diffusionszellen waren mit Wasser bzw. mit einem Gemisch aus Wasser und Lösungsmittel gefüllt.In the next step, the membrane membranes obtained for membrane transport studies were placed in diffusion cells (= transport chambers) made of stainless steel. For this purpose, the cuticles were placed with tweezers in the middle of the silicone grease-coated edges of the diffusion cells and sealed with a likewise greased ring. The arrangement was chosen so that the morphological outside of the cuticles was directed outwards, ie towards the air, while the original inside side was facing the inside of the diffusion cell. The diffusion cells were filled with water or with a mixture of water and solvent.
Zur Bestimmung der Penetration wurden jeweils 10 μl einer Spritzbrühe der in den Beispielen genannten Zusammensetzung auf die Außenseite einer Kutikula appliziert.To determine the penetration, in each case 10 μl of a spray mixture of the composition mentioned in the examples were applied to the outside of a cuticle.
In den Spritzbrühen wurden jeweils die unten in den Tabellen aufgelisteten Lösungsmittel (Leitungswasser oder einem Gemisch aus Aceton 20 Gew.-% / Leitungswasser 80 Gew.-%) verwendet.In each of the spray mixtures, the solvents listed below in the tables (tap water or a mixture of acetone 20% by weight / tap water 80% by weight) were used.
Nach dem Auftragen der Spritzbrühen ließ man jeweils das Lösungsmittel verdunsten, drehte dann jeweils die Kammern um und stellte sie in thermostatisierte Wannen, wobei auf die Außenseite der Kutikula Luft mit einer definierten Temperatur und Luftfeuchtigkeit geblasen wurde. Die einsetzende Penetration fand daher bei einer relativen Luftfeuchtigkeit von 60 % und einer eingestellten Temperatur von 20 bzw. 25 0C statt. Die Wirkstoffpenetration wurde mit radioaktiv markiertem Wirkstoff gemessen.After applying the spray liquors, the solvent was allowed to evaporate, then each turned the chambers and placed them in thermostated Tubs, where on the outside of the cuticle air was blown with a defined temperature and humidity. The onset of penetration therefore took place at a relative humidity of 60% and a set temperature of 20 and 25 0 C instead. Drug penetration was measured with radiolabeled drug.
Tabelle 1 : Förderung der Penetration verschiedener Herbizide und Safener* durch TBEP im Vergleich zur KontrolleTable 1: Promoting the penetration of various herbicides and safeners * by TBEP compared to the control
* Wirkstoff gelöst in einem Gemisch aus Aceton/ Leitungswasser (20/80 Gew.-%); ** Mittelwerte aus 4-8 Wiederholungen für die Penetration durch Apfelblattkutikeln (Temperatur = 20-250C, rel. Luftfeuchte 56-60 %); Isoxadifen-ethyl (Hersteller Bayer CropScience), Mefenpyr-diethyl (Hersteller Bayer CropScience), Cyprosulfamide (4- Cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzolsulfonamid, Hersteller Bayer CropScience), Thidiazuron (Hersteller Bayer CropScience). Wie anhand der in der Tabelle 1 aufgeführten Beispiele zu erkennen ist, führt TBEP zu einer beträchtlichen Aufnahmesteigerung der Wirkstoffe.* Active ingredient dissolved in a mixture of acetone / tap water (20/80 wt .-%); ** mean values from 4-8 repetitions for the penetration through apple leaf cuticle (temperature = 20-25 0 C, relative humidity 56-60%); Isoxadifen-ethyl (manufacturer Bayer CropScience), Mefenpyr-diethyl (manufacturer Bayer CropScience), Cyprosulfamide (4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide, manufacturer Bayer CropScience), Thidiazuron (manufacturer Bayer CropScience). As can be seen from the examples given in Table 1, TBEP leads to a considerable uptake of the active ingredients.
Tabelle 2: Vergleichsversuche verschiedener Verbindungen als Penetrationsförderer der herbiziden Wirkstoffe Fenoxaprop-P-ethyl * Table 2: Comparative experiments of various compounds as penetration promoters of the herbicidal active ingredients fenoxaprop-P-ethyl *
* Wirkstoff gelöst in einem Gemisch aus Aceton/ Leitungswasser (20/80 Gew.-%); ** Mittelwerte aus 10 Wiederholungen für die Penetration durch Apfelblattkutikeln (T = 20-250C, rel. Luftfeuchte 56-60 %); Fenoxaprop-P-ethyl (Hersteller Bayer * Active ingredient dissolved in a mixture of acetone / tap water (20/80 wt .-%); ** mean values from 10 repetitions for the penetration through apple leaf cuticles (T = 20-25 0 C, relative humidity 56-60%); Fenoxaprop-P-ethyl (manufacturer Bayer
CropScience); *** TBP = Tributylphosphat und TPP = Tripropylphosphat (Stand der Technik: EP 579052 A2); TBEP = Tributoxyethylphosphat (erfindungsgemäß).CropScience); *** TBP = tributyl phosphate and TPP = tripropyl phosphate (prior art: EP 579052 A2); TBEP = tributoxyethyl phosphate (according to the invention).
Wie anhand der in Tabelle 2 aufgeführten Beispiele zu erkennen ist, führt das erfindungsgemäße TBEP zu einer vorteilhaft höheren Aufnahmesteigerung von Wirkstoffen als die Penetrationsförderer des Standes der Technik. Dieses Ergebnis ist überraschend und war in Hinblick auf den Stand der Technik nicht zu erwarten. As can be seen from the examples given in Table 2, the TBEP according to the invention leads to an advantageously higher absorption increase of active substances than the penetration promoters of the prior art. This result is surprising and was not expected in view of the prior art.

Claims

Patentansprüche claims
1. Verfahren zur Förderung der Penetration, wobei man die Komponenten1. Method of promoting penetration, taking the components
(A) einen oder mehrere Wirkstoffe aus der Gruppe der Herbizide und/oder Safener,(A) one or more active substances from the group of herbicides and / or safeners,
(B) Tributoxyethylphosphat (TBEP) in Dosierungen von 2,5 bis 150,0 g/ha und (C) gegebenenfalls einen oder mehrere Emulgatoren, vorzugsweise aus der Gruppe der ionischen und nicht-ionischen Emulgatoren und deren Gemische mit HLB-Werten von 10 bis 17, gleichzeitig oder sequentiell auf die Schadpflanzen appliziert.(B) tributoxyethyl phosphate (TBEP) in dosages of 2.5 to 150.0 g / ha and (C) optionally one or more emulsifiers, preferably from the group of ionic and nonionic emulsifiers and mixtures thereof with HLB values of 10 to 17, applied simultaneously or sequentially to the harmful plants.
2. Verwendung des Verfahrens gemäß Anspruch 1 , wobei man die2. Use of the method according to claim 1, wherein the
Komponenten gleichzeitig oder sequentiell auf die Schadpflanzen appliziert.Components applied simultaneously or sequentially to the harmful plants.
3. Verfahren zur Bekämpfung von Schadorganismen, wobei das Verfahren gemäß Anspruch 1 , auf die Schadpflanzen appliziert wird. 3. A method for controlling harmful organisms, wherein the method according to claim 1, is applied to the harmful plants.
EP07856448A 2006-12-18 2007-12-07 Penetration enhancer for herbicides and safeners Withdrawn EP2117317A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07856448A EP2117317A2 (en) 2006-12-18 2007-12-07 Penetration enhancer for herbicides and safeners

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06026145A EP1938689A1 (en) 2006-12-18 2006-12-18 Penetration promoter for herbicides
PCT/EP2007/010643 WO2008074406A2 (en) 2006-12-18 2007-12-07 Penetration enhancer for herbicides and safeners
EP07856448A EP2117317A2 (en) 2006-12-18 2007-12-07 Penetration enhancer for herbicides and safeners

Publications (1)

Publication Number Publication Date
EP2117317A2 true EP2117317A2 (en) 2009-11-18

Family

ID=38055212

Family Applications (2)

Application Number Title Priority Date Filing Date
EP06026145A Withdrawn EP1938689A1 (en) 2006-12-18 2006-12-18 Penetration promoter for herbicides
EP07856448A Withdrawn EP2117317A2 (en) 2006-12-18 2007-12-07 Penetration enhancer for herbicides and safeners

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP06026145A Withdrawn EP1938689A1 (en) 2006-12-18 2006-12-18 Penetration promoter for herbicides

Country Status (10)

Country Link
US (1) US20100048516A1 (en)
EP (2) EP1938689A1 (en)
CN (1) CN101583281A (en)
AU (1) AU2007335005A1 (en)
BR (1) BRPI0720384A2 (en)
CA (1) CA2673033A1 (en)
CO (1) CO6220914A2 (en)
EA (1) EA200900858A1 (en)
UA (1) UA95825C2 (en)
WO (1) WO2008074406A2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1938688A1 (en) * 2006-12-18 2008-07-02 Bayer CropScience AG Penetration promoter for insecticides
US10888090B2 (en) * 2015-06-30 2021-01-12 King Abdullah University Of Science And Technology Plant growth promoters and methods of using them
US20230054152A1 (en) 2019-11-25 2023-02-23 King Abdullah University Of Science And Technology Strigolactone analogs and methods of using
CA3203568A1 (en) 2020-12-01 2022-06-09 Bayer Aktiengesellschaft Compositions comprising mesosulfuron-methyl and tehp
WO2022117515A1 (en) 2020-12-01 2022-06-09 Bayer Aktiengesellschaft Compositions comprising iodosulfuron-methyl and tehp

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2978418A (en) * 1956-02-15 1961-04-04 Switzer Brothers Inc Water emulsifiable composition
GB2022070A (en) * 1978-04-12 1979-12-12 Sandoz Ltd Defoliation compositions
JPS5724303A (en) * 1980-07-21 1982-02-08 Mitsui Toatsu Chem Inc Insecticidal composition
JPS60224606A (en) * 1984-04-23 1985-11-09 Kao Corp Effect enhancer for insecticide
DE4319263A1 (en) * 1992-07-03 1994-01-05 Schoenherr Joerg Plant treatment products
JPH08291004A (en) * 1995-04-24 1996-11-05 Nippon Kayaku Co Ltd Noxious insect controlling agent composition
US5674517A (en) * 1996-04-26 1997-10-07 Henkel Corporation Emulsifier for pesticide concentrates
DE19913036A1 (en) * 1999-03-23 2000-09-28 Aventis Cropscience Gmbh Liquid preparations and surfactant / solvent systems
DE19963381A1 (en) * 1999-12-28 2001-07-12 Aventis Cropscience Gmbh Surfactant / solvent systems
DE102004020840A1 (en) * 2004-04-27 2005-11-24 Bayer Cropscience Ag Use of Alkylcarboxamides as Penetration Promoters
GB0603891D0 (en) * 2006-02-27 2006-04-05 Syngenta Ltd Novel herbicides
EP1938688A1 (en) * 2006-12-18 2008-07-02 Bayer CropScience AG Penetration promoter for insecticides
EP1938687A1 (en) * 2006-12-18 2008-07-02 Bayer CropScience AG Penetration promoter for fungicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008074406A2 *

Also Published As

Publication number Publication date
UA95825C2 (en) 2011-09-12
AU2007335005A1 (en) 2008-06-26
BRPI0720384A2 (en) 2014-01-14
WO2008074406A3 (en) 2009-04-09
EP1938689A1 (en) 2008-07-02
WO2008074406A2 (en) 2008-06-26
CA2673033A1 (en) 2008-06-26
EA200900858A1 (en) 2009-12-30
US20100048516A1 (en) 2010-02-25
CO6220914A2 (en) 2010-11-19
CN101583281A (en) 2009-11-18
WO2008074406A4 (en) 2009-06-04

Similar Documents

Publication Publication Date Title
EP1096855B1 (en) Herbicides with substituted phenylsulfonylureas for controlling weeds in rice
KR100417509B1 (en) Herbicides containing 4-iodo-2- [3- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) ureidosulfonyl]
EP1089627B1 (en) Combination of herbicides and safeners
EP1227725B1 (en) Non-aqueous or hardly aqueous suspension concentrates of active substance combinations used for plant protection
EP2111104A2 (en) Oil suspension concentrate with micro-encapsulated agrochemical active ingredients
WO2007028505A2 (en) Novel sulfonamide-containing solid formulations
WO2008017378A2 (en) New microemulsifiable concentrates
DE10258867A1 (en) Microemulsion concentrates
EP1309241B1 (en) Use of a herbicide agent
DE10119721A1 (en) Herbicidal compositions containing benzoylcyclohexanediones and safeners
WO2007028529A1 (en) Storage-stable sulphonamide formulations
EP1523235A1 (en) Liquid adjuvants
WO2008074406A2 (en) Penetration enhancer for herbicides and safeners
EP1891855A1 (en) Novel microemulsion concentrates
DE10231615A1 (en) Fixed adjuvants
WO2007112904A1 (en) Penetration enhancers for herbicidal agents
DE10258856A1 (en) Liquid agrochemical adjuvant comprising alkoxylated polyalkyl-phenol derivative surfactant(s) and fatty acid ester(s), having synergistic effect in improving effect of active agents, especially herbicides
EP1836894A1 (en) Novel sulfonamide-containing solid formulations
DE102007013362A1 (en) Use of polyalkylene oxide for enhancing penetration of herbicidal agents into plants, for preparing plant protection agents and to combat pests and weeds

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091009

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20110303

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120703