DE3207483A1 - Substituted azolylalkyl phenoxybenzoates, processes for their preparation, and their use as herbicides - Google Patents

Abstract

Substituted azolylalkyl phenoxybenzoates of the formula <IMAGE> in which X<1> and X<2> independently of one another represent hydrogen or halogen, R<1>, R<2>, R<3> and R<4> independently of one another represent hydrogen or alkyl having 1 to 4 carbon atoms, m represents 1 or 2, n represents 0 or 1 and Az represents an optionally substituted azolyl radical, and their acid addition salts, metal salt complexes and quaternary addition salts with alkylating agents, a plurality of processes for their preparation, and their use as herbicides. Azolylalkyl phenoxybenzoates of the formula <IMAGE> in which X<1>, X<2>, R<1>, R<2>, R<3>, R<4>, Az, m and n have the meanings given above, and a process for their preparation. Halogen-substituted benzoic acid derivatives of the formula <IMAGE> in which R<1>, R<2>, R<3>, R<4>, Az, m and n have the meanings given above and Hal is fluorine, chlorine or bromine, and a process for their preparation. Phenoxybenzoyl chlorides of the formula <IMAGE> in which X<1> and X<2> have the abovementioned meanings, and a process for their preparation.

Description

Substituted phenoxybenzoic acid azolylalkyl esters, ver

drive to their manufacture and their use as herbicides The The invention relates to new substituted phenoxybenzoic acid azolylalkyl esters, several Process for their production and their use as herbicides.

It is already known that certain phenoxybenzoic acid derivatives have herbicidal properties (cf. DE-OS 2,311,638 and US Pat. No. 4,063,929). So For example, 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid, sodium salt Use (Acifluorfen) to control weeds. The herbicidal effects of this The substance is good, but the selectivity is not always sufficient.

There were now new substituted azolylalkyl phenoxybenzoates of the formula in which X1 and X2 are independently hydrogen or halogen, R¹, R², R³ and R4 are independently hydrogen or alkyl having 1 to 4 carbon atoms, m is 1 or 2, n is 0 or 1 and Az is one optionally substituted azolyl radical, and their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts found.

It has also been found that the new substituted azolylalkyl phenoxybenzoates of the formula (I), their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts are obtained if (a) substituted phenoxybenzoic acid chlorides of the formula in which X1 and X2 have the meaning given above, with hydroxyalkyl-azoles of the formula in which R1lR2 R3 R4, Az, m and n have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or (b) phenoxybenzoic acid azolylalkyl ester of the formula in which X¹, X², X¹, R2, R3, R4, Az, m and n have the meaning given above, reacted with nitric acid, optionally in the presence of a catalyst and optionally in the presence of a diluent, or (c) substituted phenols of the formula in which X1 and X2 have the meaning given above, with halogen-substituted benzoic acid derivatives of the formula in which R¹, R², R³, R4, Az, m and n have the meaning given above and Hal stands for fluorine, chlorine or bromine, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, and optionally following the one thus obtained substituted azolylalkyl phenoxybenzoate of the formula (I) an acid, a metal salt or an alkylating agent is added.

Finally, it was found that the new substituted phenoxybenzoic acid azolylalkyl ester of the formula (I), their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts characterized by very good herbicidal properties.

Surprisingly, have the substituted according to the invention Phenoxybenzoic acid azolylalkyl esters of the formula (I) and their acid addition salts, Metal salt complexes and quaternary alkylating agent addition salts are essential better selective herbicidal activity none. than the 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid sodium salt, which is a constitutionally similar, previously known Active ingredient is the same direction of action.

The substituted azolylalkyl phenoxybenzoate according to the invention are generally defined by the formula (1). In this formula are preferably X1 for chlorine, X2 for hydrogen or chlorine, R1, R2, R3 and R4 independently of one another for hydrogen or alkyl with 1 or 2 carbon atoms, m for 1 or 2, n for 0 or I and Az for a pyrazolyl, imidazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl or 1,3,4-triazolyl radical, any of these Azolyl radicals can be substituted one or more times in the same way or differently by fluorine, chlorine, bromine, iodine, alkyl with 1 to 4 carbon atoms, which in turn optionally by fluorine, chlorine, cyano, alkoxy with 1 to 4 carbon atoms, 1 to 4 carbon alkylthio.

atoms, alkylsulfinyl with 1 to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms and / or alkoxycarbonyl with 1 to 4 carbon atoms is substituted in the alkoxy group, alkoxy with 1 to 4 carbon atoms, cyano, Carboxy, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, alkylcarbonyl with 1 to 4 carbon atoms in the alkyl group and / or phenyl, which in turn optionally by halogen, alkyl having 1 to 4 carbon atoms, trifluoromethyl, Cyano, nitro and / or alkoxy is substituted with 1 to 4 carbon atoms.

Those substituted according to the invention are particularly preferred Phenoxybenzoic acid azolylalkyl esters of the formula (I) in which X is chlorine, x2 represents hydrogen or chlorine, R1 and R2 independently of one another represent hydrogen or methyl, R³ and R4 independently of one another are hydrogen or methyl stand, m stands for 1 or 2, n stands for 0 or 1 and Az stands for one via a ring nitrogen atom linked pyrazolyl, imidazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl or 1,3,4-triazolyl radical stands, where each of these azolyl radicals is one, two or three times, similar or different can be substituted by fluorine, chlorine, bromine, alkyl with 1 or 2 carbon atoms, which in turn optionally by fluorine, chlorine, cyano, alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, alkylsulfinyl with 1 or 2 carbon atoms, alkylsulfonyl with 1 or 2 carbon atoms and / or Alkoxycarbonyl is substituted by 1 or 2 carbon atoms in the alkoxy group, Alkoxy with 1 or 2 carbon atoms, alkylthio with 1 or 2 carbon atoms, Cyano, carboxy, Alkoxycarbonyl with 1 or 2 carbon atoms in the alkoxy group, alkylcarbonyl having 1 or 2 carbon atoms in the alkyl group and / or phenyl, which in turn is optionally replaced by fluorine, chlorine, bromine, alkyl with 1 or 2 carbon atoms, trifluoromethyl, cyano, nitro and / or alkoxy with 1 or 2 carbon atoms is substituted.

Acid addition salts of substituted phenoxybenzoic acid azolylalkyl esters are also preferred of formula 121234 mel (1), in which X, X, R, R, R, R, Az, m and n are those mentioned as preferred Have meanings. Particularly preferred acid addition salts are those which by addition of hydrohalic acid such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, Citric acid, salicylic acid, sorbic acid, lactic acid, and sulfonic acids, such as Example p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid are formed.

Metal salt complexes of substituted phenoxybenzoic acid azolylalkyl esters are also preferred of the formula (1), in which X, X2, R1 iR21R3, R, Az, m and n are those mentioned as preferred Have meanings. Particularly preferred are those metal salt complexes which as cations metals of the II. to IV. main group or of the I.

and II. or IV. to VIII. subgroup of the periodic table of the elements contain, with copper, zinc, manganese, magnesium, tin, iron and nickel being exemplary may be mentioned.

Anions of these metal salt complexes are preferably those which of hydrohalic acids, especially hydrochloric acid and hydrobromic acid, further derived from phosphoric acid, nitric acid and sulfuric acid.

Finally, quaternary alkylating agent addition salts are also preferred of substituted phenoxybenzoic acid azolylalkyl esters of the formula (I), in which X¹, X², R¹, R², R³, R4, Az, m and n have the meanings mentioned as preferred. Particularly preferred are those quaternary salts that are formed by the addition of Alkyl chlorides, bromides and iodides with 1 to 4 carbon atoms or from alkyl sulfates with 1 to 4 carbon atoms per alkyl group.

If 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid chloride and 1- (1-hydroxy-ethyl) -imidazole are used as starting materials, the course of process (a) according to the invention can be as follows Display formula scheme: If 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -benzoic acid (1-pyrazolyl-methyl) ester is used as the starting material, the course of process (b) according to the invention can be represented by the following equation: If 2-chloro-4-trifluoromethylphenol and 5-chloro-2-nitro-benzoic acid (1,2,4-triazol-1-yl-methyl) ester are used as starting materials, the course of the process according to the invention (c ) using the following equation: The substituted phenoxybenzoic acid chlorides required as starting materials in process (a) according to the invention are generally defined by the formula (II). In this formula, X1 and X2 preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these radicals.

Examples include 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid chloride and 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-benzoic acid chloride called.

Some of the phenoxybenzoic acid chlorides of the formula (II) have not yet been described in the literature. They are obtained in a simple manner by adding phenoxybenzoic acids of the formula in which X1 and X2 have the meaning given above, with chlorinating agents such as thionyl chloride, optionally using a catalyst such as dimethylformamide, and optionally using a diluent such as 1,2-dichloroethane, at temperatures between 1U and 1000C, and then volatile components are distilled off under reduced pressure.

The phenoxybenzoic acids of the formula (VII), - namely 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoic acid and 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-benzoic acid -, are already known (see U.S. Patent 3,928,416).

Those still to be used as starting materials in process (a) Hydroxyalkylazoles are defined by the formula (III). Have in this formula R1, R2, R3, R4, Az, m and n preferably have those meanings which are already in the context with the description of the substances of the formula (I) according to the invention preferably for these remnants were called.

Examples of hydroxyalkylazoles of the formula (III) are specifically named: 1-hydroxymethyl-pyrazole, 1 - (1 -hydroxyethyl) -pyrazole, 1-hydroxymethylimidazole, 1- (1-hydroxyethyl) imidazole, 1-hydroxymethyl-1,2,4-triazole, 1- (1-hydroxyethyl) -1,2,4-triazole, 1-hydroxymethyl-1,3,4-triazole, 1- (1-hydroxyethyl) -1,3,4-triazole, 1-hydroxymethyl-3,5-dimethylpyrazole, 1-hydroxymethyl-2-methyl-imidazole, 1-hydroxymethyl-3-methyl-pyrazole, 3-chloro-1-hydroxymethyl-1,2,4-triazole, 4-chloro-1-hydroxymethylpyrazole, 1-hydroxymethyl -4-methyl-pyrazole, 1-hydroxymethyl-4-methoxy-pyrazole, 1-hydroxymethyl-3-methylthio-pyrazole, 4-chloro-1-hydroxymethyl-3 , 5-dimethylpyrazole, 1- (2-hydroxyethyl) pyrazole, 1- (2-hydroxy-1,1-dimethyl-ethyl) pyrazole and 1- (2-hydroxyethyl) -1,2,4-triazole.

The compounds of the formula (III) are already known (cf. DE-OS 2 835 157 and 2 835 158).

Those required as starting materials in process (b) according to the invention Phenoxybenzoic acid azolylalkyl esters are generally defined by the formula (IV). In this formula, X, X2, R1, R, R, R, Az, m and n preferably have those meanings which already in connection with the description of the substances according to the invention of Formula (I) were mentioned as preferred for these radicals.

Examples of the compounds of the formula (IV) include: 3- (2-chloro-4-trifluoromethyl-phenoxy) -benzoic acid and 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -benzoic acid pyrazol-1-yl-methyl ester, -1- (pyrazol-1-yl) -ethyl ester, -imidazol-1-yl-methyl ester, -1,2,4-triazol-1-yl-methyl ester, -1,3,4-triazol-1-yl methyl ester, - (3,5-dimethylpyrazol-1-yl) methyl ester, - (2-methyl-imidazol-1-yl) methyl ester, - (3-methyl-pyrazol-1-yl) methyl ester, - (3-chloro-1, 2,4-triazol-1-yl) methyl ester, - (4-chlorpyrazol-1-yl) methyl ester, - (4-methyl-pyrazol-1-yl) methyl ester, - (4-methoxy-pyrazol-1-yl) methyl ester, - (3-methylthio-pyrazol-1-yl) methyl ester and - (4-chloro-3,5-dimethylpyrazol-1-yl) methyl ester.

The compounds of the formula (IV) have not yet been described in the literature. It is obtained by using phenoxybenzoic acid chlorides of the formula in which X1 and X2 have the meaning given above, with hydroxyalkyl-azoles of the formula in which R¹, R², R³, R4, Az, m and n have the meanings given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.

Examples of the compounds of the formula (VIII) are 3- (2-chloro-4-trifluoromethyl-phenoxy) benzoic acid chloride and 3- (2,6-dichloro-4-trifluoromethylphenoxy) benzoic acid chloride called.

The compounds of the formula (VIII) have not yet been described in the literature. However, they are obtained in a simple manner if one uses phenoxybenzoic acids of the formula in which X1 and X2 have the meaning given above, with chlorinating agents such as thionyl chloride, optionally using a catalyst such as dimethylformamide, and optionally using a diluent such as 1,2-dichloroethane, at temperatures between 10 and 1000C, reacted and then volatile components distilled off under reduced pressure.

The phenoxybenzoic acids of the formula (IX), namely 3- (2-chloro-4-trifluoromethyl-phenoxy) -benzoic acid and 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -benzoic acid, are known or can in principle known processes (see US Pat. No. 4,031,131). The phenoxybenzoic acids of the formula (IX) are thus obtained, for example, by using benzotrifluoride derivatives of the formula in which X¹ and X² have the meaning given above, with 3-hydroxybenzoic acid or its salts in the presence of an acid binder, such as potassium hydroxide or calcium hydroxide, and in the presence of a diluent such as methanol, at temperatures between 100 and 2000C.

In the above process for the preparation of the phenoxybenzoic acid azolylalkyl esters of the formula (IV) the reaction conditions correspond in detail to those of process (a) according to the invention.

Those to be used as starting materials in process (c) according to the invention substituted phenols are generally defined by the formula (V). In this Formula X1 and X2 preferably have those meanings which are already in connection with the description of the substances of the formula (I) according to the invention preferably for these remnants were called.

Examples are 2-chloro-4-trifluoromethylphenol and 2,6-dichloro-4-trifluoromethylphenol called.

The substituted phenols of the formula (V) are already known (cf. DE-OS 2 016 624).

Those in process (c) according to the invention continue to be used as starting materials required halogen-substituted benzoic acid derivatives are represented by the formula (VI) generally defined. In this formula, R¹, R², R³, R4, Az, m and n are preferably those meanings already in connection with the description of the invention Substances of the formula (I) were mentioned as preferred for these radicals.

Examples of the compounds of the formula (VI) include: 5-bromo-, 5-chloro- and 5-fluoro-2-nitro-benzoic acid pyrazol-1-yl-methyl ester, -1- (pyrazol-1-yl) -ethyl ester, -imidazol-1-yl methyl ester, -1,2,4-triazol-1-yl methyl ester, -1,3,4-triazol-1-yl methyl ester, - (3,5-dimethylpyrazol-1-yX methyl ester, - (2-methyl-imidazol-1-yii) methyl ester, - (3-methyl-pyrazol-1-yl) methyl ester, - (3-chloro-1,2,4-triazol-1-yl) methyl ester, - (4-chloro-pyrazol-1-yl) -methyl ester, - (4-methyl-pyrazol-1-yl) -methylester, - (4-methoxy-pyrazol-1-yl) -methylester, - (3-methylthiopyrazol-1-yl) methyl ester and - (4-chloro-3,5-dimethylpyrazol-1-yl) methyl ester.

The halogen-substituted benzoic acid derivatives of the formula (VI) are not yet known from the literature. However, they can be produced by conventional methods. They are obtained, for example, if 5-halo-2-nitrobenzoic acid chlorides of the formula in which Hal stands for fluorine, chlorine or bromine, with hydroxyalkyl-azoles of the formula in which R1, R2, R3, R4, Az, m and n have the meaning given above, if appropriate reacted in the presence of an acid acceptor and if appropriate in the presence of a diluent.

In the above method, the conversion conditions correspond to im individual those of process (a) according to the invention.

Process (a) according to the invention is preferably carried out in the presence carried out a diluent. As a diluent of this type, they are practically stuck all inert organic diluents in question. This includes in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as Pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, Xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ethers such as diethyl and dibutyl ethers, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones such as acetone, Methyl ethyl, methyl isopropyl and methyl isobutyl ketone, as well as esters such as methyl acetate and ethyl esters, also nitriles, such as acetonitrile and propionitrile, above in addition to amides, such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfoxide and hexamethylphosphoric acid triamide.

Acid acceptors which can be used in process (a) according to the invention all common acid binders can be used. This includes. preferably alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, also aliphatic, aromatic or heterocyclic amines, for example Triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.

The reaction temperatures can in the process according to the invention (a) can be varied within a larger range. Generally works at temperatures between -20 and -1900C, preferably between 0 and 800C. That The process is generally carried out under normal pressure.

The starting materials are used to carry out process (a) according to the invention of the formulas (II) and (III) are used in approximately equimolar amounts. A bigger one Excess of one or the other component brings no major advantages. the Implementation is carried out in a suitable diluent in the presence of a torrent of an acid acceptor. The reaction mixture is for several hours the required temperature. Working up is carried out by customary methods dutch led. Products that are crystalline at room temperature are obtained by dilution the reaction mixture with water and suction.

In another way of working up, the reaction mixture is with Water and an organic solvent that is practically immiscible with water, such as toluene added and shaken. The organic phase is separated washed with water, getiocknet, filtered and concentrated, whereby the respective Product of formula (1) is obtained as a residue.

The inventive method (b) is optionally under Performed using a diluent.

The preferred diluents are halogenated hydrocarbons, such as methylene chloride.

If appropriate, process (b) according to the invention is carried out in the presence carried out a catalyst. Protic acids are preferably used as the catalyst, such as.

Sulfuric acid or acetic acid.

The reaction temperature in process (b) is generally between -20 and + 800C, preferably kept between 0 and 500C. Procedure (b) is used in generally carried out at normal pressure.

To carry out process (b) according to the invention, one sets up 1 mol of azolylalkyl phenoxybenzoate of the formula (IV) is generally 0.9 to 2 moles, preferably 1.0 to 1.3 moles of nitric acid and optionally about the same Amount of a catalyst. The starting components are preferably under Ice cooling combined and then optionally at a slightly elevated temperature stirred until the end of the reaction.

Working up is carried out by customary methods, for example by Pour the reaction mixture into ice water, filter off with suction and, if necessary, recrystallize.

It is also possible to work as described above for method (a) has been described.

Process (c) according to the invention is preferably carried out in the presence carried out a diluent.

Suitable diluents here are preferably all of those Solvents are considered, which have already been mentioned in connection with the description of the Process (a) according to the invention have been mentioned as preferred.

Process (c) according to the invention is preferably carried out in the presence of an acid acceptor. Preferred acid acceptors are here those acid binders are considered which have already been used in connection with the Description of the inventive method (a) were mentioned as preferred.

The reaction temperatures can also be used in the process according to the invention (c) can be varied within a larger range. In general, one works at temperatures between 0 and 1000C, preferably between 10 and 800C. The inventive method (c) is generally carried out at normal pressure.

The starting materials are used to carry out process (c) according to the invention of formulas (V) and (VI) are used in approximately equimolar amounts. The implementation is generally in a suitable diluent in the presence of an acid acceptor carried out and the reaction mixture is several hours at the required Temperature stirred. Working up is by customary methods, for example as indicated above for process (a).

For the preparation of acid addition salts of the compounds of the formula (I) are preferably those acids in question that are already related with the description of the acid addition salts according to the invention as preferred acids were called.

The acid addition salts of the compounds of the formula (I) can be used in simply by using common salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g., hydrochloric acid, and in a known manner, e.g., by filtration isolated and optionally by washing with an inert organic solvent getting cleaned.

For the preparation of metal salt complexes of compounds of the formula (I) are preferably salts of those anions and cations which already in connection with the description of the metal salt complexes according to the invention were named as preferred.

The metal salt complexes of compounds of the formula (I) can be used in can easily be obtained by conventional methods, for example by dissolving the Metal salt in alcohol, e.g. ethanol, and adding to the compound of formula (I). Metal salt complexes can be used in a known manner, e.g. by filtering off or isolating and, if necessary, purify by recrystallization.

For the preparation of quaternary alkylating agent addition salts of compounds of the formula (I) are preferably those alkyl chlorides, bromides, -iodides and alkylsulphates.in bedraht, already in connection with the description of the substances according to the invention were preferably mentioned as alkylating agents.

The quaternary alkylation addition salts of the compounds of Formula (I) can be chosen in a simple manner from those customary for such alkylations Conditions are established. This is how the quaternary salts in question are obtained for example by the fact that a compound of formula (I) in an inert organic Solvent, such as acetonitrile, dissolves and the alkylating agent is added. The quaternary salts, which are obtained in crystalline form, can be separated by customary methods isolate. In general, the substances are isolated by filtering off and, if necessary purified by washing with an inert organic solvent.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, sprout inhibitors and especially used as weed repellants. Under weeds' in the broadest sense all plants are to be understood that grow in places where they are undesirable whether the inventive Fabrics as total or selective herbicides work depends essentially. of the specified amount away.

The active compounds according to the invention can be used, for example, in the following plants are used: Dicot weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocot weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active ingredients according to the invention is by no means limited to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control e.g. on industrial and Glels plants and on paths and Places with and without trees. Likewise, the compounds can be used for weed control in permanent crops e.g.

Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, Tea, rubber, oil palm, cocoa, berry fruit and hops plants and for selective Weed control can be used in annual crops.

The active ingredients according to the invention are particularly good for selective use Weed control in various crops, such as maize, soybeans, Cotton, and wheat, are suitable. In addition, they can also be used for defoliation and dehydration of the leaves are used in cotton.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, suspension emulsion concentrates, active ingredient-impregnated Natural and synthetic materials, finest encapsulation in polymer materials.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carrier materials, possibly using surface-active agents, that is, emulsifiers and / or dispersants and / or foam-generating agents.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Esters and ethers, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

The following can be used as solid carriers: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as fumed silica, alumina and Silicates; Solid carrier materials for granulates are: e.g. broken ones and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as synthetic granules from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifiers and / or foam-generating agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

These formulations generally contain between 0.1 and 90 % By weight active ingredient, preferably between 0.5 and 90%.

The active ingredients which can be used according to the invention can be used as such or in their formulations also in a mixture with known herbicides for weed control use, with ready-made formulations or tank mixes is possible. Also a mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, growth substances, Plant nutrients and soil structure improvers are possible.

The active ingredients can be used as such, in the form of their formulations or the application forms prepared therefrom by further dilution such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by watering, squirting, atomizing, Sprinkle.

The active ingredients according to the invention can both before and after Emergence of the plants are applied.

The application is preferably before the emergence of the plants, that is in the pre-emergence procedure.

They can also be incorporated into the soil before sowing.

The amount of active ingredient used can fluctuate in larger areas, it essentially depends. on the type of effect you want. In general the application rates are between 0.05 and 10 kg of active ingredient per hectare, preferably between 0.1 and 5 kg / ha.

The active compounds according to the invention show growth-regulating effects when applied afterwards Properties.

The production and use of the active ingredients according to the invention can be seen from the following examples.

Preparation examples Example 1 A solution of 20.7 g (0.05 mol) of 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-benzoic acid chloride in 30 ml of acetonitrile is added to a mixture of 5 g of 1- Hydroxymethylpyrazole, 6 g of triethylamine and 70 ml of acetonitrile were added. The mixture is stirred overnight (approx. 15 hours) at room temperature (approx. 200 ° C.).

Dana. is diluted with water and extracted with toluene.

The organic phase is washed with water, dried and filtered and narrowed. 19.3 g (81% of theory) of 5- (2,6-dichloro-4-trifauormethylphenoxy) are obtained -2-nitro-benzoic acid (1-pyrazole-methyl) ester with a melting point of 1060C as beige-colored crystalline residue.

According to the method described in Example 1 or according to the process variants (b) and (c) are the compounds listed by formulas in the tables below manufactured.

Table 1 Example X Az Melting Point (OC) No. Refractive index (nu :) 2 H -N \ 1.5638 3 H ~ 4 cl N H3C 5 H - CH3 H3C 6 Cl -N - CH3 7 H. 8 Cl -Nm Table 1 (continued) Example X2 Az melting point (° C) 20 No. Refractive index (nu :) D. 9 H '7 3N CH3 10 cl N CH3 11 H -t; C1 12 Cl C N Cl 13 H 1 XNi CH3 14 C1 N3i CH3 Table 1 (continued) Example X Az Melting Point (° C) 20 No. refractive index (nD :) 15 H -N / = 1 NI C1 16 cl N, NI cl cl 17 H - -N 18 Cl < N 19 H CH3 -NX N ~ l JzCH 20 cl Nc / OCH3 21 H -N Table 1 (continued) Example X2 Az melting point (° C) 20 No. refractive index (nD :) D. 22 Cl -N i 23 H - tNA scH3 24 Cl -Nm SCH3 H3C Cl 25 H -Ü cH3. 26 Cl H3C w Cl CH CH3 Table 2 Example X¹ X² R¹ R² R³ R4 mn Az melting point No. [° C] or Refractive dex [nD20] 27 Cl Cl HH - - 2 0 # 105 ° C 28 Cl HHH - - 2 0 # 63 ° C 29 Cl HHH CH3 CH3 1 1 # 1.5479 30 Cl Cl HH CH3 CH3 1 1 # In the following use examples, the compound given below is used as a comparison substance: (known from DE-OS 2,311,638 and US Pat. No. 4,063,929) 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoic acid, sodium salt Example A Pre-emergence test Solvent: 5 parts by weight of acetone emulsifier : 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and after Doused with the active ingredient preparation for 24 hours. You keep the amount of water expediently constant per unit area. The active ingredient concentration in the Preparation does not matter, only the application rate of the active ingredient is decisive per unit area.

After three weeks, the degree of damage to the plants is rated in % Damage compared to the development of the untreated control. It means: O% = no effect (like untreated control) 100% = total destruction in this one In the test, the active ingredients (1) and (2) according to the invention show a better selective herbicidal activity than the comparative substance (A).

Formulation example To produce a wettable powder, 50 Parts by weight of active ingredient according to Example 1, 3 "wetting agent based on alkylarylsulfonate 3 "dispersant based on ligninsulphonate 7" alkylarylsulphonate 3 "condensation product from cyclohexanone, formaldehyde and sodium bisulfite 1 "ethylenediamine tetraacetic acid disodium salt 33 "highly disperse silica mixed intensively in a Lödige mixer and then finely ground in a micronizer 8 ". The powder obtained is prior to application on the plants in the desired amount mixed with water.

Claims (10)

Claims i. Substituted phenoxybenzoic acid azolylalkyl esters of the formula in which X¹ and X2 are independently hydrogen or halogen, R1, R27R31 and R4 are independently hydrogen or alkyl having 1 to 4 carbon atoms, m is 1 or 2, n £ is 0 or 1 and Az is an optionally substituted one Azolyl radical, as well as their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts. 2. Process for the preparation of substituted phenoxybenzoic acid azolylalkyl esters of the formula in which X¹ and X² are independently hydrogen or halogen, R¹, R², R³ and R4 are independently hydrogen or alkyl having 1 to 4 carbon atoms, m is 1 or 2, n is 0 or 1 and Az is one optionally substituted azolyl radical, and their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts, characterized in that a) substituted phenoxybenzoic acid chlorides of the formula in which X1 and X2 have the meaning given above, with hydroxyalkyl-azoles of the formula in which R¹, R², R³, R4, Az, m and n have the meaning given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or b) phenoxybenzoic acid azolylalkyl ester of the formula in which X¹, X², R¹, R², R³, R4, Az, m and n have the meaning given above, reacted with nitric acid, optionally in the presence of a catalyst and optionally in the presence of a diluent, or c) substituted phenols of the formula in which X1 and X2 have the meaning given above, with halogen-substituted benzoic acid derivatives of the formula in which 234 R1, R, R, R, Az, m and n have the meaning given above and Hal stands for fluorine, chlorine or bromine, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, and optionally following the above The resulting substituted azolyl alkyl phenoxybenzoate of the formula (I) is added with an acid, a metal salt or an alkylating agent. 3. Herbicidal agents, characterized by a content of at least a substituted phenoxybenzoic acid azolylalkyl ester of the formula (I) or a Acid addition salt, metal salt complex or quaternary alkylating agent addition salt of a substituted phenoxybenzoic acid azolylalkyl ester of the formula (I). 4. Use of substituted azolylalkyl phenoxybenzoates of the formula (I) or of their acid addition salts, metal salt complexes and quaternary Alkylating agent addition salts for weed control. 5. Phenoxybenzoic acid azolylalkyl ester of the formula X1 and X2 independently represent hydrogen or halogen, R¹, R², R³ and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms, m represents 1 or 2, n represents 0 or 1 and Az represents an optionally substituted one Azolyl radical. 6. Process for the preparation of Phenoxybenzoic acid azolylalkyl esters of the formula X1 and X2 independently represent hydrogen or halogen, R¹, R², R³ and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms, m represents 1 or 2, n represents 0 or 1 and Az represents an optionally substituted one Azolyl radical, characterized in that one phenoxy-benzoic acid chlorides of the formula in which X¹ and X2 have the meaning given above, with hydroxyalkyl-azoles of the formula in which R¹, R², R³, R4, Az, m and n have the meanings given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent. 7. Halogen-substituted benzoic acid derivatives of the formula in which R¹, R², R³ and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms, m represents 1 or 2, n represents 0 or 1, Az represents an optionally substituted azolyl radical and Hal represents fluorine, chlorine or Bromine stands. 8. Process for the preparation of halogen-substituted benzoic acid derivatives of the formula in which R¹ and R² independently represent hydrogen or alkyl having 1 to 4 carbon atoms, m represents 1 or 2, n represents 0 or 1, Az represents an optionally substituted azolyl radical and Hal represents fluorine, chlorine or bromine, thereby characterized in that 5-halo-2-nitrobenzoic acid chlorides of the formula in which Hal has the meaning given above, with hydroxyalkyl-azoles of the formula in which R., R2, R3, R, Az., m and n have the meanings given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent. 9. Phenoxybenzoic acid chlorides of the formula in which X1 and X2 are independently hydrogen or halogen. 10. Process for the preparation of phenoxy-benzoic acid chlorides of the formula in which X1 and X2 are independently hydrogen or halogen, characterized in that one phenoxybenzoic acids of the formula in which X1 and X2 have the meaning given above, reacted with chlorinating agents, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent.