DE3239449A1 - Phenoxyphenyl and pyridyloxyphenyl derivatives, their preparation, agents containing them, and their use - Google Patents

Abstract

There are described novel phenoxyphenyl and pyridyloxyphenyl derivatives of the formula I defined herein <IMAGE> in which X is the fragment =CH- or =N-, R1, R2, R3 and R4 independently of one another are hydrogen, halogen, trifluoromethyl, cyano, nitro, C1-C4-alkyl or C1-C4-alkoxy, A is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon radical which has 2 to 5 carbon atoms and is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, -COOR5 or -CONR6R7, R5 is hydrogen, C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl, R6 and R7 independently of one another are hydrogen or C1-C4-alkyl, and Z is a carboxyl group or a group which can be converted into a carboxyl group, including their salts, with the proviso that X represents the fragment =N- when A denotes the vinylene group -CH=CH-, and the preparation of these compounds. The active substances of the formula I or agents containing them can be used for controlling undesirable plant growth.

Description

Phenoxyphenyl and pyridyloxyphenyl derivatives, process for their preparation

position, agents containing them and their use.

The present invention relates to new phenoxyphenyl and pyridyloxyphenyl derivatives, Process for their preparation, means using the derivatives as the active component contain, and the use of the derivatives or agents containing them for combating of unwanted vegetation.

The phenoxyphenyl and pyridyloxyphenyl derivatives according to the invention correspond to the general formula I. where X is the fragment = CH- or = N-, R1, R2, R3 and R4 independently of one another hydrogen, halogen, trifluoromethyl, cyano, vitro, C1-C4-alkyl'or C1-C4-alkoxy, A is a straight-chain or branched one, Saturated or unsaturated, unsubstituted or substituted by halogen, cyano, C 1-C4-alkoxy, Cl-C4-alkylthio, C -C -alkylcarbonyl, -COOR or 14 14 5 -CONR6R7 aliphatic hydrocarbon radical with 2 to 5 carbon atoms, R hydrogen, C1-C4-alkyl, C2-C4-alkenyl or 5 carbon atoms, 4 hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, R6 and R7 independently of one another are hydrogen or C1-C4-alkyl, and Z a carboxyl group or a group which can be converted into a carboxyl group, including their salts, with the proviso that X stands for the fragment = N- when A denotes the vinylene group -CH = CIS-.

Araliphatic carboxylic acid derivatives with pharmacological effects and their production are in the patent publications DE-OS 19 41 625, DE-OS 24 58 375, DE-OS 25 09 891, DE-OS 25 28 958, DE-OS 27 09 268, GB-PS 1,278,406 and US-PS 3,739,015 have been described. Furthermore, araliphatic carboxylic acid derivatives are considered synthetic juvenile hormones and process for their production known from Helvetica Chimica Acta, Vol. 58 (1), 1975, 268-278, 278-283, 283-292, 293-296. The production of cinnamic acid derivatives, which are suitable for controlling pests known from DE-OS 21 62 571. Aliphatic acid derivatives, which by phenoxyphenoxy or pyridyloxyphenoxy groups are substituted and have a herbicidal effect, are in the patent publications DE-OS 26 23 558, DE-OS 27 15 284, US-PS 4,046,553, U.S. Patent 4,213,774 and EP-A 3114. Also a herbicidal activity have the 2-nitro-styrene derivatives described in Japanese Patent Publication 75 / 135.220 on.

It has now been found that compounds of the formula I according to The present invention is excellent for controlling undesirable vegetation suitable.

In the compounds of the formula I, halogen represents fluorine, chlorine or bromine or iodine.

As alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.

Butyl, tert-butyl or isobutyl can be considered.

Alkoxy stands for methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy or isobutoxy.

Under alkylthio are methylthio, ethylthio, n-propylthio, isopropylthio, To understand n-butylthio, sec-butylthio, tert-butylthio or isobutylthio.

The hydrocarbon radical A is above all alkylene, alkenylene and alkynylene groups with 2 to 5 carbon atoms which are unsubstituted or substituted by halogen, cyano, C1-C4 -alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, -COOR5 or -CONR6R7 Consider, in particular, an alkylene or alkenylene group in which R12, R13, R14 and R15 independently of one another denote hydrogen, halogen or unsubstituted or halogen-substituted Cl-C3-alkyl or one of the symbols R12, 13'14 and R15 also denote C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, cyano, -COOR5, -CONR6R7 or C1-C3-alkyl substituted by C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylcarbonyl, cyano, -COOR5 or -CONR6R7, or R12 and R13 together also mean a bond between the carbon atoms to which they are attached.

For example, -CHCl-CHCl-, -CH (CH3) -CH (CH3) -, -CH (CH3) -CH2-CHC1-CH2-, -CH (CONH2) -CH2-, -C-C-, -CH (CH3) -CH2-, -CH2-CH2-CH (OCH3) -CH2-, -CH (CH3) -CHBr-, -C (CH3) = C (CH3) -, -CH2-CH (COOH) -CH2-, -CH2-CH (CH3) -, -C (CH3) = CH-C (CH3) -, -CH2-CH (CH2OH) -, -CH2-CH (CN) -CH2-CH2-, -CHF-CH2-, -CH2-CHC1 -, - CH2-CH (COSC2H5) -CH2-, -CHCl-CH = CH-CH2-, -CH2-CH (CHO) -CH2-, -CH [CON (CH3) 2 1 -CH2-, -CH2-CH (OC2H5) -s -CH2-CCl (CH3) -, -CH2-CH (COOC2H5) -CH2-, -CH2-CH (COOCH3) -, -CH2-CHBr-, -CH = C (CH3), -CH = C (SCH3) -, -CH = C (CN) - and -OH = C (COOC2H5) - into consideration.

In the compounds of the formula I, alkenyl is preferably allyl, Alkynyl preferred for propargyl.

A group Z which can be converted into a carboxyl group is, for example to understand one of the following groups: -CN, -COOR8> -COSR9 and -CONR10R11, wherein R8 and Rg are C1-C4-alkyl, C2-C4-alkenyl or C2-C4-alkynyl and Rg are also hydrogen and R10 and Rll independently from one another hydrogen, Cl-C4-alkyl or are C1-C4-alkoxy; the salts of the free carboxylic acid with the ammonium cation, a metal cation, in particular an alkali or alkaline earth metal cation, or with an organic nitrogen base. Magnesium, for example, can be used as metal cations, Calcium, lithium and preferably potassium or sodium can be considered. Examples of for Organic nitrogen bases suitable for salt formation are primary, secondary and tertiary, aliphatic and aromatic, optionally hydroxylated on the hydrocarbon radical Amines such as methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers Butylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, Pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tri-n-propylamine, Quinuclidine, pyridine, quinoline, isoquinoline, as well as methanolamine, ethanolamine, propanolamine, Dimethanolamine, diethanolamine or triethanolamine can be considered, as well as the quaternary ones Ammonium bases are tetraalkylammonium, in which the alkyl radicals are, independently of one another, straight-chain or branched C1-C4-alkyl groups, such as tetramethylammonium, tetraethylammonium or trimethylethylammonium, as well as trimethylbenzylammonium, triethylbenzylammonium and trimethyl-2-hydroxyethylammonium. The present invention includes stereoisomers and racemates of compounds of formula I.

Preference is given to compounds of the formula I in which X has the meaning given for formula I, R1 is hydrogen or halogen, R2 is halogen or trifluoromethyl, R3 is hydrogen and R4 is hydrogen or halogen, A is an ethynylene group or an alkylene or alkenylene group wherein R12 for hydrogen, R13 for hydrogen or halogen or R12 and R13 together for a bond between the carbon atoms to which they are attached, R14 for hydrogen, Cl-C3-alkyl, halogen or -CH (CN) -COOCl-C4-alkyl and R15 stands for hydrogen, C1-C3-alkyl, halogen, cyano, O1-O4-alkylthio, a C1-C3-alkyl substituted by a cyano group or -COOR5, in which R5 stands for C1-C4-alkyl, and Z denotes for -COOCH, -CN, -COOR8, in which R8 is Cl-C4-alkyl, or for -CONRloRll, in which R10 and R11 independently of one another are hydrogen or Cl-C4-alkyl or one of the symbols R10 and R11 is also a Cl-C4- Alkoxy group means, stands, or the salt of the free carboxylic acid with a quaternary ammonium base or an alkali metal cation.

Of these compounds, those of particular interest are in which R1 is in the ortho and R2 in the para position to the nitrophenoxy group.

Particular preference is given to compounds of the formula I in which X has the meaning given for formula I, R1 is hydrogen, chlorine or bromine, R2 is chlorine or trifluoromethyl, R3 is hydrogen and R4 is hydrogen or chlorine, A is an ethynylene group or an alkylene - or alkenylene group where R12 for hydrogen, R13 for hydrogen or chlorine or R12 and R13 together for a bond between the carbon atoms to which they are bonded, R14 for hydrogen, methyl or chlorine and R15 for hydrogen, methyl, chlorine, cyano, methylthio, ethylthio, Cyanomethyl or -OOOR5, where R5 is methyl or ethyl, or R14 is -cH (cN) -coOc2H5 and R12, R13 and R15 are hydrogen, and Z is -COOH, -CN, -COOR8, where R8 Cl-C4-alkyl denotes, -CONH2, -CON (CH3) 2, -CON (C2H5) 2 or -CON (CH3) -OCH3, or the salt of the free carboxylic acid with the ammonium or potassium cation. Of these compounds, those in which R1 is in the ortho and R2 in the para position to the nitrophenoxy group are in the foreground.

Very particular preference is given to compounds of the formula I in which X has the meaning given for formula I, R 1 is chlorine, R 2 is chlorine or trifluoromethyl, R 3 is hydrogen and R 4 is hydrogen or chlorine, A is an alkylene or alkylene group wherein R12 represents hydrogen, R13 represents hydrogen or chlorine or R12 and R13 together represent a bond between the carbon atoms to which they are bonded, R14 represents hydrogen, R15 represents hydrogen or one of the two symbols R14 and R15 represents methyl, and Z is -COOR8, in which R8 is methyl or ethyl. Of these compounds, particular emphasis should be given to those in which R1 is in the ortho and R2 in the para position to the nitrophenoxy group.

Particularly preferred compounds are: 2-methyl-3- [2'-nitro-5 1 (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl] -propionic acid methyl ester 2- [2'-nitro-5 '- (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl] -n-butyric acid methyl ester 2-Methyl-3- [2'-nitro-5 '- (3', 5 "-dichloropyridyl-2" -oxy) -phenyl] -acrylic acid, methyl ester 2-Methyl-3- [2'-nitro-5 '- (3 "-chloro-5" -trifluoromethylpyridyl-2 "-oxy) -phenyl] -acrylic acid methyl ester Ethyl 2-chloro-3- [2'-nitro-5 '- (2 "-chlor-4" -trifluoromethylphenoxy) phenyl] propionate Ethyl 2-chloro-3- [2'-chloro-3 '- (2 ", 4" -dichlorophenoxy) -6'-nitrophenyl] propionate Methyl 2-chloro-2-methyl-3- [2'-nitro-5'- (2 "-chlor-4" -trifluoromethylphenoxy) phenyl] propionate Methyl 2-methyl-3- [2 -nitro-5 - (3 "-chlor-5" -trifluoromethylpyridyl-2 "-oxy) phenyl] propionate.

The preparation of compounds of the formula I can be according to the Perform the procedure described below.

A) The compounds of the formula I can be prepared by adding a compound of the formula II in which X, R1, R2 and R3 have the meanings given for formula I and D stands for a halogen atom or a hydroxyl group, in the presence of a base with a compound of the formula III wherein R4, A and Z have the meanings given for formula I, Q stands for hydrogen or the nitro group and E stands for a halogen atom or a hydroxyl group, where in formulas II and III one of the symbols D and E stands for a halogen atom and the other represents a hydroxyl group, and, when Q represents hydrogen, nitrates the compound obtained.

B) Compounds of the formula I in which A is a halogenated hydrocarbon radical having 2 to 5 carbon atoms wherein R16 and R17 independently represent hydrogen, halogen, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, -COOR5 or -OONR6R7 or a straight-chain or branched, saturated or unsaturated, unsubstituted or halogen, cyano, Cl-C4 -Alkoxy, Cl-C4-alkylthio, -COOR5 or -CONR6R7 substituted aliphatic hydrocarbon radicals having 1 to 3 carbon atoms and R5, R6 and R7 have the meanings given for formula I can also be prepared by adding a compound of the formula IV in which X, R1, R2, R3 and R4 have the meanings given for formula I, Q stands for hydrogen or the nitro group and Hal stands for a halogen anion, with a compound of the formula V in the presence of copper salts in which R16 and R17 have the meanings given above and Z has the meanings given for formula I, reacted and, if Q is hydrogen, nitrated the compound obtained.

C) Compounds of the formula I in which A is an unsaturated hydrocarbon radical having 2 to 5 carbon atoms wherein R18 is hydrogen or methyl and R19 is hydrogen, cyano, 0r0 4-alkylthio, -COOR5 or -CONR6R7 or methyl or ethyl which is unsubstituted or substituted by halogen, cyano, Cl-C4-alkoxy -COOR5 or -CONR6R7 and R5, R6 and R7 have the meanings given for formula I, can also be prepared by adding a compound of the formula VI in which X, R1, R2, R3 and R4 have the meanings given for formula I, R18 has the meaning given above and Q stands for hydrogen or the nitro group, in the presence of a basic catalyst with a compound of the formula VII R19-OH2-Z ( VII) in which R19 has the meaning given above and Z has the meaning given for formula I, is reacted and, if Q is hydrogen, the compound obtained is nitrated.

D) Compounds of the formula I in which A is an ethynylene radical can be prepared by adding a compound of the formula VIII in which X, R1, R2, R3 and R4 have the meanings given for formula I, Hal stands for a halogen atom and Q stands for hydrogen or the nitro group, in the presence of a catalyst in a basic medium with a compound of the formula IX HC-CZ (IX ) wherein Z has the meaning given for formula I, and, when Q is hydrogen, nitrated the compound obtained.

The nitration of compounds obtained in which Q is hydrogen can be carried out in a manner known per se, for example by treatment with nitric acid or a nitric acid / sulfuric acid mixture.

In compounds of the formula I obtained, the hydrocarbon radical A can be converted into another radical A defined under formula r, for example by hydrogenation, by addition or subtraction of hydrogen halide or halogen or by decarboxylation.

The substituent Z can also be used in compounds of the formula I, for example, by hydrolysis, alcoholysis, aminolysis or by salt formation with an ammonium cation, a metal cation or an organic nitrogen base in another substituent Z defined under formula I can be converted.

In addition, there may be substituents in the compounds of the formula I obtained be introduced within the framework of the definitions given, for example by post-chlorination.

The reactions are expediently in an organic solution or Diluent carried out. Examples are aromatic and aliphatic Hydrocarbons such as benzene, toluene, xylenes, petroleum ether, cyclohexane, n-hexane; halogenated hydrocarbons such as chlorobenzene. Methylene chloride, ethylene chloride, Chloroform, carbon tetrachloride, tetrachlorethylene; Alcohols, especially aliphatic Alcohols such as methanol, ethanol, propanol, butanol; Ether and ethereal compounds such as dialkyl ethers (diethyl ether, diisopropyl ether); N, N-dialkylated amides such as dimethylformamide; Dimethyl sulfoxide; Ketones such as acetone, diethyl ketone, methyl ethyl ketone and mixtures such solvents with each other.

The reactions can be carried out at room temperature but preferably at reflux temperature. In general, the implementations carried out under normal pressure or slightly increased pressure.

Organic and inorganic bases are suitable as bases. Suitable Bases are, for example, alkali metal hydroxides, such as sodium or potassium hydroxide, Alkali or alkaline earth metal carbonates, ammonia, secondary or tertiary amines such as Trialkylamines (trimethylamine, triethylamine, tripropylamine), pyridine or pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine).

The basic catalysts are, for example, ammonia, primary or secondary amines, but especially pyridine with a trace of piperidine.

The catalysts for process D) are, in particular, meta, .lcatalysts into consideration, preferably palladium salts or complexes, such as especially palladium chloride PdC12, palladium acetate (Pd (OCOCH3) 2 or the palladium dichlorobis (triphenylphosphine) complex PdC12 [P (C6H5) 3] 2, usually with the addition of a copper (I) salt, in particular copper (I) iodide. The catalysts are used as such or raised on a usual Carriers such as carbon powder or alumina are used.

The starting substances are known or can be known analogously Process.

Starting compounds of the formula III can be prepared analogously to the processes given under B, C and D above: a) Compounds of the formula III in which A is a halogenated hydrocarbon radical having 2 to 5 carbon atoms wherein R16 and R17 independently represent hydrogen, halogen, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, -COOR5 or -CONR6R7 or a straight-chain or branched, saturated or unsaturated, unsubstituted or halogen, cyano, Cl-C4 -Alkoxy, Cl-C4-alkylthio, -COOR5 or -CONR6R7 substituted aliphatic hydrocarbon radical with 1 to 3 carbon atoms and R5> R6 and R7 have the meanings given for formula III, can be prepared by adding a compound of the formula IIIa wherein R4 has the meaning given for formula III, Hal represents a halogen atom, Hal ° represents a halogen anion and Q represents hydrogen or the nitro group, in the presence of copper salts with a compound of the formula V in which R16 and R17 have the meanings given above and Z has the meanings given for formula III, are reacted and, if Q is hydrogen, the compounds obtained are optionally nitrated.

b) Compounds of the formula III in which A is an unsaturated hydrocarbon radical having 2 to 5 carbon atoms wherein R18 represents hydrogen or methyl and R19 represents hydrogen, cyano, C1-O4-alkylthio, -COOR5 or -CONR6R7 or methyl or ethyl which is unsubstituted or substituted by halogen, cyano, Cl-C4-alkoxy, -COOR5 or -CONR6R7 and R5 , R6 and R7 have the meanings given for formula I, can also be prepared by adding a compound of the formula IIIb wherein R4 and E have the meanings given for formula III, R18 has the meaning given above and Q is hydrogen or the nitro group, in the presence of a basic catalyst with a compound of the formula VII R19-CH2-Z (VII) in which R19 is the above given meaning and Z have the meaning given for formula III, and, if Q is hydrogen, the compound obtained is nitrated if necessary.

c) Compounds of the formula III in which A is an ethynylene radical can be prepared by adding a compound of the formula IIIc wherein R4 has the meaning given for formula III, Hal stands for a bromine or iodine atom and Q stands for hydrogen or the nitro group, in the presence of a catalyst in a basic medium with a compound of the formula IX HC-CZ (IX) wherein Z is the has the meaning given for formula III, and, if Q is hydrogen, the compounds obtained are optionally nitrated.

The diazonium salts of the formula IV can be carried out analogously to known processes by diazotizing the corresponding amino compounds in the presence of a hydrohalic acid can be obtained. In an analogous manner, the compounds of the formula IIIa getting produced.

For application as herbicides, the compounds of formula 1 in unchanged form or preferably together with those in formulation technology common auxiliaries and are therefore used, for example, in emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted Emulsions, wettable powders, soluble powders, dusts, granulates, including encapsulations processed in e.g. polymeric materials in a known manner.

The application methods such as spraying, misting, dusting, scattering, Brushing or pouring will be the same as the type of Means the chosen according to the desired goals and the given circumstances.

The formulations, i.e. the active ingredient of the formula I and optionally agents, preparations or containing a solid or liquid additive Compositions are prepared in a known manner, for example by intimate mixing and / or grinding the active ingredients with extenders, such as solvents, solid carriers, and optionally surface-active compounds (surfactants).

The following solvents can be used: aromatic hydrocarbons, preferably the fractions C8 to C12, such as xylene mixtures or substituted naphthalenes, Phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized Coconut oil or soybean oil, or water.

As solid carriers, e.g. for dusts and dispersible powders, As a rule, natural rock flour is used, such as calcite, talc, kaolin, Montmorillonite or Attapulgite. To improve physical properties Highly disperse silica or highly disperse absorbent polymers can also be added will. As granular, adsorptive granulate carriers, porous types such as pumice stone, Broken bricks, sepiolite or bentonite, as non-sorptive carrier materials e.g. calcite or sand in question. In addition, a large number of pregranulated materials can be used inorganic or organic nature such as in particular dolomite or crushed Plant residues are used.

The surface-active compounds come, depending on the type of the to be formulated Active ingredient of the formula I with nonionic, cationic and / or anionic surfactants good emulsifying, dispersing and wetting properties. Among surfactants are also to understand surfactant mixtures.

Suitable anionic surfactants can be so-called water-soluble soaps like water soluble synthetic surface active compounds.

The soaps are alkali, alkaline earth or optionally substituted Ammonium salts of higher fatty acids (C10-C22), e.g.

the Na or K salts of oleic or stearic acid, or of natural ones Fatty acid mixtures called, e.g. obtained from coconut or tallow oil can. The fatty acid methyl laurine salts should also be mentioned.

However, so-called synthetic surfactants are used more frequently, in particular Fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical 8 to 22 carbon atoms, where alkyl also includes the alkyl part of acyl radicals, e.g. the Na or Ca salt of ligninsulphonic acid, the dodecylsulphuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids.

This subheading also includes the salts of sulfuric acid esters and sulphonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives contain preferably 2 sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkyl aryl sulfonates are e.g. the Na, Oa or triethanolamine salts of dodecylbenzenesulfonic acid, the Dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

There are also corresponding phosphates such as salts of the phosphoric acid ester a p-nonylphenol- (4-14) -ethylene oxide adduct in question.

Polyglycol ether derivatives are primarily used as nonionic surfactants of aliphatic or cycloaliphatic alcohols, saturated or unsaturated Fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms may contain in the alkyl radical of the alkylphenols.

Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethyleneoxy adducts and polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the compounds mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, Castor oil glycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, Polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned.

Furthermore, there are also fatty acid esters of polyoxyethylene sorbitan like that Polyoxyethylene sorbitan trioleate into consideration.

The cationic surfactants are mainly quaternary Ammonium salts which contain at least one alkyl radical with 8 to 22 as N-substituent Contain carbon atoms and, as further substituents, n-edered, optionally halogenated Have alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are, among others, in the following publications described: "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood New Jersey, 1980 Sisely and Wood, "Encyclopedia of Surface Active Agents, "Chemical Publishing Co., Inc. New York, 1980 The Agrochemical Preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, of active ingredient of formula I, 99.9 to 1%, in particular 99.8 to 5% of a solid or liquid Additive and 0 to 25%, in particular 0.1 to 25%, of a surfactant.

While concentrated products are preferred as commodities, the end user usually uses diluted agents.

The agents can also contain other additives such as stabilizers, defoamers, Viscosity regulators, binders, adhesives and fertilizers or other active ingredients included to achieve special effects.

The new compounds of formula I have a pronounced herbicidal, optionally also selective herbicidal activity. The active ingredients or them Containing agents can be used to control weeds both by the pre-emergence method (pre-emergent) as well as post-emergent and are for example for the selective control of weeds in crops of Cotton, legumes, in particular soy, root crops, maize, rice, millet, wheat and other grains.

Example 1: 20 g of 2-nitro-5- (2'-chloro-4'-trifluoromethylphenoxy) aniline are concentrated in 40 ml of water, 75 ml of glacial acetic acid and 16 ml. Hydrochloric acid dissolved and hot then with ice cooling at 0-5 ° C with a solution of 4.25 g of sodium nitrite diazotized in 10 ml of water. After removing the excess nitrite with sulfamic acid becomes the reaction solution filtered and stored at 20-30 ° C with stirring in a solution of 75 ml of acetone, 4 g of copper (II) chloride, 4 ml of 30% sodium hydroxide solution and 5 g of ethyl acrylate were added dropwise. After about an hour when the lively Gas evolution has ended, the mixture is mixed with water and in several Portions extracted with ethyl acetate.

The combined extracts are washed with water. After drying the solution over sodium sulfate and evaporation leaves an oily residue by chromatography on a silica gel column with ethyl acetate / hexane 1: 9 as mobile phase 8.5 g of ethyl 2-chloro-3- [2 -nitro-5 '- (2 "-chlor-4" -trifluoromethylphenoxy) phenyl] propionate (Compound No. 1) can be obtained. M.p. 58-600C.

Example 2: The method given in Example 1 gives using 5 g of methyl methacrylate instead of ethyl acrylate and of methyl acetate instead of ethyl acetate 3.5 g of 2-chloro-2-methyl-3- Methyl [2'-nitro-5 '- (2 "-chlor-4" -trifluoromethylphenoxy) phenyl] propionate 25 (compound no. 2) as a yellowish oil. nD 1.5405.

Example 3: 6.8 g (0.02 mol) of 2-methyl-3- [3 '- (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl] -acrylic acid methyl ester are dissolved in 30 ml of ethylene chloride and cooled to 0 ° C. Become this solution at 0 ° C 7 ml conc.

Sulfuric acid and then 0.8 ml of 100% nitric acid were added dropwise. The mixture is stirred for 11/2 hours without cooling, then the reaction mixture is up Poured ice and extracted with methylene chloride. The methylene chloride phase is washed with water, dried with magnesium sulfate and evaporated. The firm one The residue is recrystallized from ethyl acetate / hexane. 4 g (52 % of theory) 2-methyl-3- [2 '-nitro-5'- (3 ", 5" -dichloropyridyl-2 "-oxy) -phPnyl] -acrylic acid methyl ester (Compound No. 3). M.p. 132-134 ° C.

The following compounds of the formula I listed in Table 1 together with compounds 1 to 3 can also be prepared in an analogous manner: Table 1 phys. No. X Rl R2 -RB RL AZ a ~ data 1 OH- 2-C1 4-CF3 HH -CH -CH- COOC2H5 m.p. 58-60 ° C CHg 2 OH- 2-C1 4-OF3 HH -CH - ¢ - -COOCH3 n25 1.5405 D. 3 = N- 3-01 5-01 HH OH = H3 -OO0OH3 m.p. 132-1340O FH ÇH3 4 = N- 3-C1 5-C1 HH CH2-CH- -COOCH3 m.p. 78-810O 5 = N- 3-C1 5-CF3 HH -CH = C- -COOCH3 nD 1.5543 3 D 6 OH- 2-01 4-01 H 6-01 OH2-H -O00O2H5 Sdp.2500O / 0, lIR 7 = N- 3-C1 5-C1 HH -CH-CH- -COOCH3 ng 1.5827 8 = N- 3-C1 5-CF3 HH -CH2-CH- - 30cd3 nD 1.5247 3 9 OH- H 4-CF3 HH -CH2s [- -COOC4Hgn 3 43 10 OH- 2-C1 4-CF3 HH-CH = C- -CN 11 = N- 3-C1 5-C1 HH -CC- -COOCH3 physics No. X R1 R2 RRAZ table 3 -4 .DaLeri. CHs 12 OH- 2-C1 4-CF3 HH -C = CH- -CONH2 CH3 13 OH- 2-C1 4-CF3 HH -CH = C- -CN 1 14 OH- 2-Br 4-CF3 HH -OH2-H- COOC3H7iso 15 = N- 3-C1 5-CF3 HH -CC- -COOCH3 16 = N- 3-C1 5-C1 HH -CH = CH- -COOC2H5 FHs 17 OH- 2-C1 4-C1 HH 'CH2'C' COOCH3 C1 C1 FI 18 OH- 2-C1 4-C1 HH -CH-CH- -CON (CH3) 2 19 = N- 3-C1 5-CF3 HH -CH = CH- -COOC2H5 3 20 OH-2-C1 4-C1 HH -CH = C- -CN CN -CN 21 OH-2-C1 4-C1 HH -CH = C- -CN 22 OH- 2-C1 4-CF3 HH-CH = C- -CN 23 OH- 2-C1 4-C1 HH -CH = C- -COOCH3 C1 24 = N- 3-C1 5-C1 HH -CH -CH- -COOC2H5 L. 25 = CH-2-C1 4-C1 HH CH = C -COOC2H5 FH3 CN 26 OH- 2-C1 4-CF3 HH -C = C- -CN CN m.p. 133- 27 = N- 3-C1 -5-C1 HH -CH = C- -COOC2H5 1340C Physics tab No. X R1 R2 R3 4 AZ data 4th 28 = CH-2-C1 4-CF, EH3 28 OH- 2-C1 4-OF3 HH-CH = C- -CN CN 29 OH-H 4-CF 3 HH -CH = - -CN N m.p. 126- 30 = N- 3-C1 5-CF3 HH-CH = C- COOC2H5 127 ° C 3 31 = N- 3-C1 5-C1 HH -CH---COOC2H5 C1 32 = CH-2-C1 4-C1 HH -CH = C- -CON (C2H5) 2 -252 33 OH- 2-01 4OF3 HH -OH2-- -ON NC-cH-COOC, HS NC-ÇH-COOC2X5 34 OH- 2-C1 4-CF3 HH-OH2- -COOC2H5 2 35 = N- 3-C1 5-C1 HH -CH2-CH- -CN 2 ÇOOCH3 36 = CH- 2-G1 4-CF3 HH CH2-CH-COOCH3 CH2CN 37 OH- 2-C1 4-C1 HH -CH2-CH- -CN 38 OH- 2-C1 4-CF3 HH -CR, -CH2- -COO "NH4 3 39 OH- 2-C1 4-CF HH -OH 'CHZK ~ CN FH 40 OH- 2-C1 4-CF3 HH ~ CH ~ 3 -O0N (OH3) -OCH3 3 3 3 41 = N- 3-C1 5-C1 HH -CH - H1- -COOC2H, No. X R1 R2 R3 R4 AZ physical data -CH, -COO OT 0 42 OH- 2-C1 4-CF3 HH -CH = C- -COO K CN 43 OH- 2-C1 4-C1 HH -OH2-OH- -COOC2Hg 44 = CH-H 4-CF 3 HH -CH -CH - -COOH COCH3 45 = N- 3-01 5-OF3 HH -CH = C- -COOC2H5 and 1.5527 STILL, -0000 H nD 1.5982 1 3 25 46 = N-3-C1 5-C1 HH -CH = C 0000 2H5 47 = N- 3-C1 5-C1 HH -CH = C -COOC2H5 m.p. 58-610C ICOOC2H5 25th 48 = N- 3-C1 5-CF3 HH -CH = C- -COOC2H5 m.p. 66-72 ° C CgOOCH3 49 = CH- 2-C1 4-CF3 HH -CH = C- -COOCH3 m.p. 166-168 ° C Cl 50 = N- 3-C1 5-C1 HH -CHZCH- -CONH2. M.p. 131-134 ° C Formulation examples for liquid active ingredients of formula I (% = weight percent) 4. Emulsion concentrates a) b) c) Active ingredient from Table 1 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol AeO ) 5% - -Tributylphenol polyethylene glycol ether - 12% 4% (30 mol AeO) cyclohexanone 15% 20% xylene mixture 65% 25% 20% By diluting with water, emulsions of any desired concentration can be produced from such concentrates.

5. Solutions a) b) c) d) Active ingredient from Table 1 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% - - -Polyethylene glycol M G 400 - 70% - -N-methyl-2-pyrrolidone - 20% - -Epoxidised coconut oil - - 1% 5% petrol (boiling point 160-1900C) - - 94% -The solutions are suitable for use in the form of tiny drops.

6. Granules a) b) Active ingredient from Table 1 5% 10 X kaolin 94% highly dispersed Silicic acid 1% -attapulgite - 90 z The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent then evaporated off in vacuo.

7. Dusts a) b) Active ingredient from Table 1 2% 5% highly dispersed Silicic acid 1% 5% talc 97% kaolin - 90% by mixing the carriers thoroughly with the active ingredient, ready-to-use dusts are obtained.

Formulation examples for solid active ingredients of the formula I (% = percent by weight) 8. Wettable powder a) b) c) Active ingredient from Table 1 25% 50% 75% N-lignosulfonate 5% 5% Na lauryl sulphate 3% - 5% Na diisobutyl naphthalene sulphonate - 6% 10% octylphenol polyethylene glycol ether (7-8 mol AeO) - 2% -Highly disperse silica 5% 10% 10% kaolin 62% 27% -Der Active ingredient is mixed well with the additives and placed in a suitable mill grind well. You get wettable powders, which can be mixed with water to form suspensions Allow to dilute the desired concentration.

-9. Emulsion concentrate active ingredient from Table 1 10% octylphenol polyethylene glycol ether (4-5 mol AeO) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (35 mol AeO) 4% cyclohexanone 30% xylene mixture 50% This concentrate can be diluted emulsions of any desired concentration can be made with water.

10. Dusts a) b) Active substance from Table 1 5% 8% Talc 95% -Kaolin - 92% Ready-to-use dusts are obtained by adding the active ingredient mixed with the carrier substances and ground on a suitable mill.

11. Extruder granules, active ingredient from Table 1, 10% Na lignosulfonate 2% carboxymethyl cellulose 1 Z kaolin 87% The active ingredient is with the additives mixed, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

12.- Coating granulate active ingredient from Table 1 3% polyethylene glycol (M G 200) 3% kaolin 94% The finely ground active ingredient is in evenly applied to the kaolin moistened with polyethylene glycol using a mixer. In this way, dust-free coating granules are obtained.

13. Suspension concentrate active ingredient from Table 1 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol AeO) 6% sodium lignin sulfonate 10% carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil in the form of a 75% aqueous Emulsion 0.8% water 32% The finely ground active ingredient is mixed with the additives intimately mixed. A suspension concentrate is obtained in this way, from which by diluting suspensions of any desired concentration can be prepared with water.

Example 14: Pre-emergent herbicidal action (germ inhibition) in the greenhouse is immediately after sowing the seeds of test plants in seed trays Earth's surface with an aqueous dispersion of active ingredients of the formula I obtained made from 25% wettable powder. There are concentrations of 4 kg of active substance applied per hectare. The seed trays are in the greenhouse at 22-25 ° C and 50-70 % relative humidity kept. The experiment is evaluated after 3 weeks and the results are rated according to the following rating scale: 1 = plants not germinated or totally dead 2-3 = very strong effect 4-6 = medium effect 7-8 = little effect 9 = no effect (like untreated control) the Compounds of the formula I show a good effect in this test.

For example, the following results were obtained for compounds no. 1 and 2 against the weeds Sinapis, Setaria and Stellaria: Table 2 Connection Nt. ! Sinapis Setaria Stellaria 1 1 1 2 2 1 1 2 Example 15: Pre-emergent herbicidal action (sprout inhibition) Under the conditions specified in Example 14, a test is carried out with a larger number of crop plants and weeds, using concentrations of 4 kg and 2 kg of active ingredient per hectare. The results are rated according to the rating scale given in Example 14.

The compounds of the formula I show a good selective herbicidal action in this test. For example, the following results were obtained for compounds No. 1 and 2: Table 3 Connection No. 1 connection No. 2 Test plant application rate Application rate 4 kg / ha. 2 kg / ha 4 kg / ha i2 kg / ha Wheat 6 7 7 8 Corn 9 9 9 9 Dry rice 9 9 - 7 9 Alopecurus myos. 2 3 2 3 Echinochloa cg 1 6 1 2 Rottboellia ex. -2 2 7 1 3. Soy 8 9 7 8 Cotton 7 8 4 6 Abutilon 1 1 1 1 Chenopodium res. 1 1 1 1 Ipomoea 1 5 1 3 Sinapis 1 1 1 1 Viola tricolor 1 1 1 1 Example 16: Post-emergent herbicidal action (contact herbicide) The weeds to be tested are after emergence (in the 4- to 6-leaf stage) with an aqueous dispersion of active ingredients of the formula I, obtained from a 25% wettable powder, in a Dosage of 4 kg of active ingredient per hectare was sprayed onto the plants and kept at 24-26 ° C. and 45-60% relative humidity. After 15 days, the experiment is evaluated and the result is rated on the same scale as in the pre-emergent experiment (example 14).

The compounds of the formula I show a good effect in this test.

For example, the following results were obtained with compounds No. 1 and 2: Table 4 Link. Setaria Solanum Sinpis Stellaria Phaseolus No. 1 1 1 1 2 '1 2 2 1 1 3 2 I. Example 17: Post-emergent herbicidal action (contact herbicide) Under the conditions given in example 16, a test is carried out with a large number of crop plants and weeds, concentrations of 0.25 kg and 0.12 kg of active ingredient per hectare being used. The results are rated according to the rating scale given in Example 14.

The compounds of the formula I show a good selective herbicidal action in this test. For example, the following results were obtained for compound no. 2: Table 5 Test plant application rate 0.25 kg / ha 0.12 kg / ha Barley 7 8 Wheat 7 8 Corn 8 9 Sorghum hybr. 7 7 Rice dry 8 - 9 Soy 7 8 Abutilon 1 1 Xanthium 1 3 Amaranthus ret. 1 1 Solanum nigrum 1 2 Ipomoea 1 1 Sinapis 1 1 Crysanthemum. leuc. 1 1 Galium aparine 2 3 Viola tricolor 1 1 Veronica Sp. 1 1

Claims (1)

Claims 1. Compounds of Formula 1 where X-the ~ fragment = CH- or = N-, R1, R29, R3 and R4 independently of one another hydrogen, halogen, trifluoromethyl, cyano, Nitto, Cl-C4-alkyl or C1-C4-alkoxy, A is a straight-chain or branched one, Saturated or unsaturated, unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy, Cl-C4-alkylthio, C1-C4-alkylcarbonyl, -COOR5 or -CONR6R7-substituted aliphatic hydrocarbon radical with 2 to 5 carbon atoms, R5 hydrogen, C1-C4- Alkyl, C2-C4-alkenyl or C2-C4-alkynyl, R6 and R7 independently of one another are hydrogen or C 1-C4-alkyl, and Z denotes a carboxyl group or a group which can be converted into a carboxyl group, including their salts, with the proviso that X stands for the fragment = N- when A is the vinylene group -CH = CH-. 2. Compounds of formula I according to claim 1, characterized in that X has the meaning given for formula I, R1 is hydrogen or halogen, R2 is halogen or trifluoromethyl, R3 is hydrogen and R4 is hydrogen or halogen, A is an ethynylene group or an alkylene or alkenylene group wherein R12 for hydrogen, R13 for hydrogen or halogen or R12 and R13 together for a bond between the carbon atoms to which they are attached, R14 for hydrogen, Cl-C3-alkyl, halogen or -CH (CN) -COOC1-Clp- A1kyl and R15 stand for hydrogen, C1-C3-alkyl, halogen, cyano, C1-C4-alkylthio, a C 1-C3-alkyl or -COOR5 substituted by a cyano group, in which R5 stands for C1-C4-alkyl , and Z for -COOH, -CN, -COOR8, in which R8 is Cl-C4-alkyl, or for -CONR R 1, in which R10 and R11 are independently hydrogen or C 1 -C 4 -alkyl or one of the symbols R10 and R11 also denote a C1-C4-alkoxy group, or the salt of the free carboxylic acid with a quaternary ammonium base or an alkali metal cation. 3. Compounds of formula I according to claim 1, characterized in that X has the meaning given for formula I, R1 is hydrogen, chlorine or bromine, R2 is chlorine or trifluoromethyl, R3 is hydrogen and R4 is hydrogen or chlorine, A is a Ethynylene group or an alkylene or alkenylene group where R12 for hydrogen, R13 for hydrogen or chlorine or R12 and R13 together for a bond between the carbon atoms to which they are bonded, R14 for hydrogen, methyl or chlorine and R15 for hydrogen, methyl, chlorine, cyano, methylthio, ethylthio, Cyanomethyl or -CoOR5, where R5 is methyl or ethyl, or R14 is -CH (CN) -COOC2H5 and R12, R13 and R15 are hydrogen, and Z is -COOH, -CN, -COOR8, where R8C1 -C4-Alkyl means, -CONH2, -CON (CH3) 2, -CON (C2H5) 2 or -CON (CH3) -OCH3, or the salt of the free carboxylic acid with the ammonium or potassium cation. 4. Compounds of formula I according to claim 1, characterized in that X has the meaning given for formula I, R1 is chlorine, R2 is chlorine or trifluoromethyl, R3 is hydrogen and R4 is hydrogen or chlorine, A is an alkylene or alkenylene group wherein R12 represents hydrogen, R13 represents hydrogen or chlorine or R12 and R13 together represent a bond between the carbon atoms to which they are bonded, R14 represents hydrogen, R15 represents hydrogen or one of the two symbols R14 and R15 represents methyl, and Z is -COOR8, in which R8 is methyl or ethyl. 5. Compounds of formula I according to one of claims 2 to 4, characterized characterized in that R1 is in the ortho and R2 in the para position to the nitrophenoxy group stand. 6. 2-Methyl-3- [2'-nitro-5'- (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl ] methyl propionate. 7. 2- [21 -nitro-51 - - (3'g, 5 "-dichloropyridyl-2" -oxy) -phenyl] -n-butyric acid methyl ester 8. 2-Methyl-3- [2V-nitro-5 '- (3 ", 5" - dichloropyridyl-2 "- oxy) -phenyl] -acrylic acid, methyl ester. 9. 2-Methyl-3- [2 '-nitro-5 P - (3 "-chlor-5" -tr if luo rme thy Ipyridyl-2 "-oxy) -phenyl] -acrylic acid-methyl ester. 10. Ethyl 2-chloro-3- [2 1-nitro-5 1 (211-chloro-4'1-trifluoromethylphenoxy) phenyl] propionate. 11. 2-Chloro-3- [21-chloro-3 - (2 ", 4" -dichlorophenoxy) -6 -nitrophenyl] -prop Ionic acid ethylacetate. 12. 2-chloro-2-methyl-3-t2'-nitro-5 '- (2 "-chlor-4" -trifluoromethylphenoxy) phenyl] propionic acid methyl ester. 13. 2-Methyl-3- [2'-nitro-5 '- (3 "-chlor-5" -trifluoromethylpyridyl-2 "-oxy) -phenyl] -propionic acid methyl ester. 14. Process for the preparation of compounds of the formula I, characterized in that a compound of the formula II in which X, R1, R2 and R3 have the meanings given for formula I and D stands for a halogen atom or a hydroxyl group, in the presence of a base with a compound of the formula III wherein R4, A and Z have the meanings given for formula I, Q stands for hydrogen or the nitro group and E stands for a halogen atom or a hydroxyl group, where in formulas II and III one of the symbols D and E stands for a halogen atom and the other represents a hydroxyl group, and, when Q represents hydrogen, nitrates the compound obtained. 15. Process for the preparation of compounds of the formula I in which A is a halogenated hydrocarbon radical having 2 to 5 carbon atoms wherein R16 and R17 independently represent hydrogen, halogen, cyano Cl-C4-alkoxy, CC-alkylthio, -COOR5 or straight-chain or -C1-C4 -alkylthio, -COOR5 or -C0NR R or a straight-chain or branched, saturated or unsaturated, unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy, Cl-C4-alkylthio, -COOR5 or -CONR6R7 aliphatic hydrocarbon radical with 1 to 3 carbon atoms and R5, R6 and R7 have the meanings given for formula I, means thereby characterized in that a compound of the formula IV wherein X, R1, R2, R3 and R4 have the meanings given for formula I, Q stands for hydrogen or the nitro group and Hal # for a halogen anion, in the presence of copper salts with a compound of the formula V in which R and R17 have the meanings given above and Z 16 has the meanings given for formula I, are reacted and, if Q is hydrogen, the compound obtained is nitrated. 16 Process for the preparation of compounds of the formula I in which A is an unsaturated hydrocarbon radical having 2 to 5 carbon atoms wherein R18 is hydrogen or methyl and R19 is hydrogen, cyano, C1-C4-alkylthio, -COOR5 or -CONR6R7 or methyl or ethyl which is unsubstituted or substituted by halogen, cyano, C1-C4-alkoxy, -COOR5 or -CONR6R7 and R5, R6 and R7 have the meanings given for formula I, means, characterized in that a compound of the formula VI wherein X, R1, R2, R3 and R have the meanings given for formula I, R18 has the meaning given above and Q stands for hydrogen or the nitro group, in the presence of a basic catalyst with a compound of the formula VII R19-CH2-Z ( VII) in which R19 has the meaning given above and Z has the meaning given for formula I, is reacted and, if Q is hydrogen, the compound obtained is nitrated. 17. A process for the preparation of compounds of the formula I in which A is an ethynylene radical, characterized in that a compound of the formula VIII in which X, R1, R2, R3 and R4 have the meanings given for formula I, Hal stands for a halogen atom and Q stands for hydrogen or the nitro group, in the presence of a catalyst in a basic medium with a compound of the formula IX HC = CZ (IX ) in which Z has the meaning given for the formula I, and, if Q is hydrogen, the compound obtained is nitrated. 18. Herbicidal agent, characterized in that it is considered active Component contains at least one compound of the formula I according to claim 1. 19. Means according to claim 18, characterized in that it is 0.1 to 99 percent by weight of a compound of the formula I according to claim 1, 1 to 99.9 percent by weight of additives and 0 to 25 percent by weight of a surfactant. 20. Means according to claim 19, characterized in that it is 0.1 to 95 percent by weight of a compound of the formula I according to claim 1, 5 to 99.8 percent by weight of additives and 0.1 to 25 percent by weight of a surfactant. 21. Means according to claim 18, characterized in that it is considered active Component 2-methyl-3- [2 '-nitro-5' - (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl] -propionic acid, methyl ester contains. 22. Means according to claim 18, characterized in that it is considered active Component 2- [2'-nitro-5 '- (3 ", 5" -dichloropyridyl-2 "-oxy) -phenylj-n-butyric acid, methyl ester contains 23. Agent according to claim 18, characterized in that it is considered active Component 2-methyl-3- [2'-nitro-5P- (3 ", 5" -dichloropyridyl-2 "-oxy) -phenyl] -acrylic acid-methyl ester contains. 24. Means according to claim 18, characterized in that it is considered active Component 2-Hethyl-3- [2v-nitro-5 '- (3 "-chlor-5" -trifluoromethylpyridyl-2 "-oxy) -phenyl] -acrylic acid-methyl ester contains. 25. Composition according to claim 18, characterized in that it is considered active Component 2-chloro-3- [2 '-nitro-5' - (2 "-chlor-41, -trifluoromethylphenoxy) -phenyl [-propionic acid ethyl ester contains. 26. Means according to claim 18, characterized in that it is considered active Component ethyl 2-chloro-3- [2'-chloro-3 '- (2 ", 4" -dichlorophenoxy) -6'-nitrophenyl] propionate contains. 27. Composition according to claim 18, characterized in that it is considered active Component 2-chloro-2-methyl-3- [2 '-nitro-5' - (2 "-chlor-4" -trifluoromethylphenoxy) -phenyl] -propionic acid methyl ester contains. 28. Means according to claim 18, characterized in that it is considered active Component 2-methyl-3- [2'-nitro-5 '- (3 "chloro-5" -trifluoromethylpyridyl-2 "-oxy) -phenyl] -propionic acid methyl ester contains. 29. A process for the production of herbicidal compositions, characterized in that that one or more compounds of the formula I according to claim 1 together with solid or liquid carriers and / or surfactants intimately mixed. 30. Use of compounds of formula I according to claim 1 or agents containing them for controlling undesired vegetation. 31. Use according to claim 30 for the selective control of weeds in crops. 32. Use according to claim 31 for the selective control of weeds in crops of cereals. 33. Use according to claim 31 for the selective control of weeds in millet. 34. Use according to claim 31 for the selective control of weeds in wheat. 35. Use according to claim 31 for the selective control of weeds in rice. 36. Use according to claim 31 for the selective control of weeds in corn. 37..Use according to claim 31 for the selective control of weeds in cotton. 38. Use according to claim 31 for the selective control of weeds in root crops. 39. Use according to claim 31 for the selective control of weeds in legumes. 40. Use according to claim 39 for the selective control of weeds in soy. 41. A method for controlling unwanted vegetation, thereby characterized in that a compound of the formula I according to claim 1 or an agent which contains a compound of the formula I, on plants, their locations or Plant parts applied.