DE3122175A1 - Substituted azolylalkyl phenoxyphenoxyalkanecarboxylates, processes for their preparation, and their use as herbicides and plant growth regulators - Google Patents

Abstract

Substituted azolylalkyl phenoxyphenoxyalkanecarboxylates 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 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 and plant growth regulators. Azolylalkyl haloalkanecarboxylates of the formula <IMAGE> in which R<1>, R<2>, R<3>, R<4> and Az have the abovementioned meaning, and Hal represents chlorine or bromine, and their preparation. Compounds of the formula <IMAGE> in which X<1>, X<2>, R<1>, R<2>, R<3>, R<4> and Az have the abovementioned meaning, and their preparation.

Description

Substituted phenoxyphenoxyalkanecarboxylic acid azolyl

alkyl esters, process for their preparation and their use as Herbicides and Plant Growth Regulators The invention relates to new substituted ones Phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester, several processes for their preparation and their use as herbicides and plant growth regulators.

It is already known that certain phenoxyphenoxyalkanecarboxylic acid esters have herbicidal properties (cf. DE-OS 2,311,638 and US Pat. No. 4,093,446). So for example q <- (5- (2-chloro-4-trirluoromethylphenoxy) -2-nitro-phenoxy) -Use ethyl propionate to control weeds. The effect of this The substance is good, but the selectivity is not always sufficient.

There were now new substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula in which X1 and X2 independently represent hydrogen or halogen, R1, R2, R3 and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms and Az represents an optionally substituted azolyl radical, as well as their acid addition salts, metal salt complexes and quaternaries Alkylating agent addition salts found.

It has also been found that the new substituted azolylalkyl phenoxyphenoxyalkanecarboxylates of the formula (I), their acid addition salts, metal salt complexes and quaternary alkylating agent addition salts are obtained if a) phenoxyphenoxyalkanecarboxylic acid chlorides of the formula in which X1, X2, R1 and R2 have the meaning given above, with hydroxylalkylazoles of the formula in which R3, R4 and Az have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if b) phenoxyphenols of the formula are reacted in which X1 and X2 have the meaning given above with haloalkanecarboxylic acid azolylalkyl esters of the formula in which R1, R2, R3 and R4 and Az have the meaning given above and Hal stands for chlorine or bromine, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, or when c) phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of the formula in which X1, X2, R1, R2, R3, R4 and and Az have the meaning given above, reacted with nitric acid, optionally in the presence of a catalyst and optionally in the presence of a diluent, and optionally then followed by the phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of the formula (I) an acid, a metal salt or an alkylating agent is added.

Finally, it was found that the new substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of formula (I) and their acid addition salts, metal salt complexes and quaternary Alkylating agent addition salts through excellent herbicidal and plant growth regulating Characteristics distinguish.

Surprisingly, have the substituted according to the invention Phenoxyphenoxyalkanecarboxylic 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 effectiveness than oC- (5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy) -propionic acid ethyl ester, which is a constitutionally similar previously known active ingredient with the same direction of action is. In addition, the substances according to the invention can also be used as plant growth regulators insert. Most importantly, they can be used as defoliants and desiccants on cotton will.

The substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters according to the invention are through the Formula (I) generally defined. In this formula X1 preferably represents chlorine, X2 represents hydrogen or chlorine, R1, R2, R3 and R4 independently of one another for hydrogen or methyl and Az for one via a ring nitrogen atom bonded pyrazolyl, imidazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl or 1,3,4-triazolyl radical, where each of these azolyl radicals is one or more identical or different can be substituted 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, alkylthio with 1 to 4 carbon atoms, alkylsulfinyl with 1 up to 4 carbon atoms, alkylsulfonyl with 1 to 4 carbon atoms and / or alkoxycarbonyl is substituted with 1 to 4 carbon atoms in the alkoxy group, alkoxy with 1 up to 4 carbon atoms, alkylthio 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 Particularly Those substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters according to the invention are preferred of the formula (I), in which x1 stands for chlorine, X2 stands for hydrogen or chlorine, R1 represents methyl, R2, R3 and R4 represent hydrogen and Az represents one over one Ring nitrogen atom bonded pyrazolyl, imidazolyl, 1,2,4-triazolyl, 1, 2,3-triazolyl- or 1,3,4-triazolyl radical, each of these azolyl radicals being one, two or can be substituted three times, identically or differently by fluorine, chlorine, Bromine, alkyl with 1 or 2 carbon atoms, which in turn, optionally through 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 with 1 or 2 carbon atoms is substituted in the alkoxy group, alkoxy of 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 possibly by fluorine, Chlorine, bromine, alkyl with 1 or 2 carbon atoms, trifluoromethyl, cyano, nitro and / or alkoxy is substituted by 1 or 2 carbon atoms.

Acid addition salts of phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters are also preferred of the formula (I) in which X1 x2 R1 R2 R3 R4 and Az have the meanings mentioned as preferred to have. Those acid addition salts which are formed by addition are particularly preferred of hydrohalic acid, such as hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example Acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, Sorbic acid, lactic acid, and sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulphonic acid are formed.

Metal salt complexes of phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters are also preferred of the formula (I), in which X1, X2, R1, R2, R3, R4 and Az are preferably mentioned 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 phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula (1), in which X1, X2, R1, R2, R3, R4 and Az have the meanings mentioned as preferred. Particularly Those quaternary salts which are obtained by addition of alkyl chlorides or bromides are preferred and iodides each with 1 to 4 carbon atoms or dialkyl sulfates with 1 up to 4 carbon atoms per alkyl group are formed.

If Cc- (5-2-chloro-4-trifluoromethylphenoxy) -2-nitro-phenoxy) -prionic acid chloride and 1-hydroxymethylpyrazole are used as starting materials, the course of process (a) according to the invention can be represented by the following equation: If 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-phenol and pyrazolyl-methyl Oc -bromopropionate are used as starting materials, the course of process (b) according to the invention can be as follows Display formula scheme: If α - (3- (2-chloro-4-trifluoromethyl-phenoxy) -phenoxy) -propionic acid-pyrazolyl-methyl ester is used as the starting material and nitric acid as the nitrating agent, the course of process (c) according to the invention can be represented by the following equation : Formula (II) provides a general definition of the phenoxyphenoxyalkanecarboxylic acid chlorides required as starting materials in process (a) according to the invention. In this formula, X1, X2, R1 and R2 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 are 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy-acetic acid chloride, 5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy-acetic acid chloride, c'c - (5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy) -propionic acid chloride and OL- (5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy) -propionic acid chloride called.

The compounds of the formula (II) are already known (cf. DE-OS 2 906 237).

Those still to be used as starting materials in process (a) Hydroxyalkylazoles are defined by the formula (III). Have in this formula R31, R4 and Az 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 mentioned.

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-triaz.ol, 1-hydroxymethyl-3,5-dimethyl-pyrazole, 1-hydroxymethyl-2-methyl-imidazole, 1-hydroxymethyl-3-methyl-pyrazole, 3-chloro-1-hydroxymethyl-1 2,4-triazole, 4-chloro-1-hydroxymethyl-pyrazole, 1-hydroxymethyl-4-methyl-pyrazole, 1-hydroxymethyl-4-methoxy-pyrazole, 1-hydroxymethyl-3-methylthio-pyrazole and 4-chloro 1-hydroxymethyl-3,5-dimethyl-pyrazole.

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 Phenoxyphenols are generally defined by the formula (IV). 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 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenol and 5- (2,6-dichloro-4-trifluoromethylphenoxy) -2-nitro-phenol called.

The compounds of the formula (IV) are already known (cf. US Pat 3,928,416).

Those still to be used as starting materials in process (b) The formula (V) provides a general definition of haloalkanecarboxylic acid azolylalkyl esters.

In this formula, R1, R2, R3, R4 and Az. Preferably have those Meanings already in connection with the description of the invention Substances of the formula (I) were mentioned as preferred for these radicals.

Hal in formula (V) represents chlorine or bromine.

Examples of the compounds of the formula (V) include: bromoacetic acid, Chloroacetic acid, bromopropionic acid and α-chloropropionic acid pyrazol-1-ylmethyl 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-dimethyl-pyrazol-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-chloro-pyrazol-1-yl) -methylester, - (4-methyl-pyrazol-1-yl) -methylester, - (4-methoxypyrazol-1-yl) -methylester, - (3-methylthiopyrazol-1-yl) methyl ester and - (4-chloro-3,5-dimethylpyrazol-1 -yl) methyl ester.

The compounds of the formula (V) have not yet been described in the literature. However, they can be produced in a simple manner by methods known per se.

They are obtained, for example, when using halocarboxylic acid halides of the formula in which R1 and R2 have the meaning given above and Hal and Hal 'are chlorine or bromine, with hydroxyalkylazoles of the formula in which R3, R4 and Az have the meanings given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

The halocarboxylic acid halides required as starting materials in the above process are defined by the formula (VII). In this formula, R1 and R2 preferably have those meanings already in connection with the description of the invention Substances of the formula (1) were mentioned as preferred for these residues. Hal and Hal ' stand for chlorine or bromine.

Examples of the compounds of the formula (VII) are chloroacetyl chloride, Bromoacetyl chloride, bromoacetyl bromide, cc -chloropropionic acid chloride, -bromopropionic acid chloride and called oC-bromopropionic acid bromide.

The compounds of the formula (VII) are known.

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

Those required as starting materials in process (c) according to the invention Phenoxyphenoxy-alkanecarboxylic acid azolylalkyl esters are general by the formula (VI) Are defined. In this formula, X1, X2 R1, R2, R3, R4 and Az preferably have 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: 3- (2-chloro-4-trifluoromethyl-phenoxy) - and 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -phenoxyacetic acid and - α-phenoxy-propionic 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-chloro-pyrazol-1-yl) -methyl ester, - (4-methyl-pyrazol-1-yl) -methylester, - (4-methoxypyrazol-1-yl) methyl ester, - (3-methylthio-pyrazol-1-yl) methyl ester and - (4-chloro-3,5-dimethyl-pyrazol-1-yl) methyl ester.

The compounds of the formula (VI) have not yet been described in the literature; however, they can be produced in a simple manner by processes known per se. They are obtained, for example, when one uses phenoxyphenols of the formula in which X1 and X2 have the meaning given above, with haloalkanecarboxylic acid azolylalkyl esters of the formula in which R1 2 3 4, R, R3, R4, Az and Hal have the meaning given above, if appropriate reacted in the presence of an acid acceptor and if appropriate in the presence of a diluent.

The phenoxyphenols required as starting materials in the above process are defined by the formula (VIII). In this formula, X1 and X2 preferably have 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 (VIII) are 3- (2-chloro-4-trifluoromethyl-phenoxy) -phenol and 3- (2,6-dichloro-4-trifluoromethyl-phenoxy) -phenol called.

The compounds of the formula (VIII) are already known (cf. DE-OS 2 805 981).

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

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

Practically all inert organic diluents can be used as such diluents Solvent in question. These include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, Petroleum ether, gasoline, ligroin, benzene, toluene, methylene chloride, ethylene chloride, chloroform, Carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, furthermore ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, also esters, such as methyl and ethyl acetate, and nitriles, such as e.g. acetonitrile and propionitrile, in addition amides such as dimethylformamide, Dimethylacetamide and N-methyl-pyrrolidone, as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

Acid acceptors which can be used in process (a) according to the invention all common acid binders can be used. These preferably include 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) within a larger range can be varied. In general one works at temperatures between -20 and + 1000C, preferably between 0 and 800C.

Process (a) according to the invention is in general carried out under normal pressure carried out.

When carrying out process (a) according to the invention, one uses to 1 mole of phenoxyphenoxyalkanecarboxylic acid chloride of the formula (II) in general 0.9 to 1.5 mol, preferably 1.0 to 1.3 mol of hydroxyalkylazole of the formula (III) and optionally 1 to 1.5 moles, preferably 1.05 to 1.3 moles of acid acceptor. Because the slightly exothermic course of the reaction, the starting components are preferred put together under ice cooling and then at a slightly higher temperature until the end the implementation stirred. Working up is carried out by customary methods. It will for example diluted with toluene, washed with water, dried, filtered and narrowed. The products left behind are characterized by their melting point characterized.

Process (b) according to the invention is preferably carried out in the presence carried out by diluents. Preferred diluents are here all those solvents are considered which are already in connection with the description of process (a) according to the invention have been mentioned as preferred.

Process (b) according to the invention is preferably carried out in the presence carried out by acid acceptors. Preferred acid acceptors are here those acid-binding agents which have already been taken into account in connection with the description of process (a) according to the invention have been mentioned as preferred.

Never reaction temperatures can also in the case of the invention Process (b) can be varied over a wide range. Generally works one at temperatures between 0 and 1000C, preferably between 10 and 800C.

Process (b) according to the invention is in general carried out under normal pressure carried out.

When carrying out process (b) according to the invention, one uses to 1 mole of phenoxyphenol of the formula (IV) in general 0.9 to 1.5 moles, preferably 1.0 to 1.3 mol of haloalkanecarboxylic acid azolylalkyl ester of the formula (V) and optionally 1 to 1.5 moles, preferably 1.05 to 1.3 moles of acid acceptor.

The starting materials are combined at room temperature and if necessary stirred at a slightly elevated temperature until the reaction has ended. The work-up is carried out by customary methods, for example as described above.

Process (c) according to the invention is optionally used carried out a diluent.

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

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

Sulfuric acid or acetic acid.

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

To carry out process (c) according to the invention, one sets up 1 mole of azolylalkyl phenoxyphenoxyalkanecarboxylate of the formula (VI) in general 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 preferred combined with ice cooling and then optionally at a slightly elevated temperature stirred until the end of the reaction.

Working up is by customary methods, for example by Pouring into ice water, suctioning off and, if necessary, recrystallizing carried out.

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 filtering off, 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 alkyl sulphates which have already been considered in connection with the description of the substances according to the invention were preferably mentioned as alkylating agents.

The alkylating agent quaternary addition salts of the compounds of the 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 having 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 killers. Under weeds in In the broadest sense, all plants are to be understood that grow in places where they are are undesirable. Whether the substances according to the invention as total or selective herbicides act depends essentially on the amount used.

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 rail systems 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, 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 grain, suitable.

The active ingredients according to the invention also have a very good one plant growth regulating effectiveness. They are particularly suitable for inhibiting growth, as well as for defoliation and drying of the leaves of cotton.

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

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. 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 ethers and esters, 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; with liquefied gaseous extenders or carriers such liquids are meant which are at normal temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons and butane, Propane, nitrogen and carbon dioxide, as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, such as highly dispersed Silica, alumina and silicates; come as solid carriers for granules in question: e.g. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic or organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foam-producing 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 and latex-like polymers are used such as gum arabic, polyzinyl 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.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known herbicides or plant growth regulators for Weed control or as plant growth regulators are used, finished formulations or tank mixes are 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 from it by further dilution prepared application forms, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granulates can be applied. It is used in the usual way, e.g. by pouring, Spraying, spraying, scattering.

The active compounds according to the invention can be used as herbicides can be applied both before and after emergence of the plants. The application is preferred before emergence of the plants, i.e. in the pre-emergence method, performed. They can also be incorporated into the soil before sowing.

For the use of the active compounds according to the invention as plant growth regulators applies that the application is carried out in a preferred period of time, its exact Delimitation is based on the climatic and vegetative conditions.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general are the application rates between 0.01 and 50 kg of active ingredient per hectare of soil area, preferably between 0.05 and 10 kg per ha.

The production and use of the active ingredients according to the invention is evident from the following examples.

Preparation examples Example 1 A solution of 21.2 g (0.05 mol) of S - (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-phenoxy) propionic acid chloride in 30 ml of toluene is converted into a mixture cooled to 0 to 50 ° C 5.4 g (0.055 mol) of 1-hydroxymethylpyrazole, 6 g (0.06 mol) of triethylamine and 70 ml of toluene were added.

The reaction mixture is left overnight (approx. 15 hours) at room temperature (approx. 200C) stirred. For work-up, it is diluted with toluene, then with water, dilute sodium hydroxide solution and washed again with water, dried, filtered and constricted. 17.0 g (70% of theory) ° C- (5- (2-chloro-4-trifluoromethylphenoxy) -2 are obtained Pyrazol-1-yl methyl nitrophenoxy) propionate in the form of beige crystals with a melting point of 750C.

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

Table 1 Example X Az melting point No. OC - 2 C1 -NxN 1 124 3 H. 4 cl H 5 H H3 + CH3 6 Cl H3Cx H3 CH3 7 H / = » 8 C1 -NuN i 9 H. CH3 T? Ln CH3 Table 1 (continued) Example X Az melting point No. "C 10 Cl -D CH3 r = N 11 H ~ | N <Cl r = rN 12 C1 hl- C1 13 H. CH3 14 cl N < CH3 15 Mr. N 5 cl 16 cl N ffi cl cl 17 H -y e Table 1 (continued) Example X Az melting point No. OC C1 F. 18 cl N <CH3 19 H. Wzl 20 cl N ocn, 21 H -Nu / = Tr-OCH 22 cl 23 H. SCH3 24 Cl - 'ICCH, SCH3 H3> Cl 25 H. CH, H, C C1J HC Cl 26 Cl 3) = t -NN \ CH3 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. 4,093,446) ethyl α- (5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitro-phenoxy) -propionate, Example A, pre-emergence test Solvent: 5 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient 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: 0% no effect (like untreated control) 100% total destruction In this remainder show the active ingredients according to the invention (1) and (2) a better selective herbicidal activity than the comparative substance (A).

Example B Defoliation and drying out of the leaves in cotton Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To produce an appropriate preparation of active ingredient, 1 part by weight is mixed Active ingredient with the specified amounts of solvent and emulsifier and fill with water on the desired concentration.

Cotton plants are grown in the greenhouse until the 5. Follower sheet tightened. At this stage the plants will become dripping wet with the Sprayed active ingredient preparations. After 1 week, the leaf fall and drying out of the leaves rated in comparison to the control plants. It means: 0 none Leaves dry out, no leaf fall + leaves dry out slightly, less Leaf fall ++ strong drying out of the leaves, strong leaf fall +++ very strong Drying out of the leaves, very severe leaf fall. In this test, those according to the invention show Active ingredients (1) and (2) have a very strong effectiveness.

Claims (11)

Claims 1. Substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula in which X1 and X2 independently represent hydrogen or halogen, R1, R2, R3 and R4 independently represent hydrogen or alkyl with 1 to 4 carbon atoms and Az represents an optionally substituted azolyl radical, as well as their acid addition salts, metal salt complexes and alkylating agent quaternary addition salts. 2. Substituted Phenoxyphenoxyalkanecarbonsäureazolylalkylester der Formula (I), in which X1 stands for chlorine, x2 stands for hydrogen or chlorine, R1 , R2, R3 and R4 independently represent hydrogen or methyl and Az for a pyrazolyl, imidazolyl, 1, 2,4-triazolyl, bonded via a ring nitrogen atom, 1,2,3-triazolyl or 1,3,4-triazolyl radical, each of these azolyl radicals can be substituted one or more times, identically 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, alkylthio with 1 up to 4 carbon 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 of 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, cyano, carboxy, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl group and / or phenyl, which in turn, optionally by halogen, alkyl with 1 to 4 carbon atoms, trifluoromethyl, cyano, nitro and / or alkoxy with 1 to 4 carbon atoms is substituted, as well as their acid addition salts, metal salt complexes and quaternary Alkylating agent addition salts. 3. Process for the preparation of substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula in which X1 and X2 independently represent hydrogen or halogen, R1, R2, R3 and R4 independently represent hydrogen or alkyl with 1 to 4 carbon atoms and Az represents an optionally substituted azolyl radical, as well as their acid addition salts, metal salt complexes and quaternary Alkylating agent addition salts, characterized in that (a) phenoxyphenoxyalkanecarboxylic acid chlorides of the formula in which X1, X2, R1 and R2 have the meaning given above, with hydroxyalkylazoles of the formula in which R3, R4 and Az have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or that (b) phenoxyphenols of the formula in which x1 and X2 have the meaning given above with haloalkanecarboxylic acid azolylalkyl esters of the formula in which R1, R2, R3 and R4 and Az have the meaning given above and Hal is chlorine or bromine, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, or that (c) phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of the formula in which X1, X, X21R1, R2, R3, R4 and Az have the meanings given above, reacted with nitric acid, optionally in the presence of a catalyst and optionally in the presence of a diluent, and optionally then followed by the phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula (I ) an acid, a metal salt or an alkylating agent is added. 4. Herbicides and plant growth regulators, marked by a content of at least one substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of formula (I) or an acid addition salt, metal salt complex or quaternary Alkylating agent addition salt of a substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of formula (I). 5. Method of combating weeds and regulating the Plant growth, characterized in that substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of formula (I) or their acid addition salts, metal salt complexes or quaternary Alkylating agent addition salts on the weeds or the plants to be regulated and / or their habitat. 6. Use of substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of formula (I) or of their acid addition salts, metal salt complexes and quaternaries Alkylating agent addition salts for weed control and regulation of plant growth. 7. Process for the production of herbicidal resp. Plant growth regulating agents, characterized in that one substituted phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula (I) or their acid addition salts, metal salt complexes or quaternary alkylating agent addition salts mixed with extenders and / or surfactants. 8. Haloalkanecarboxylic acid azolylalkyl esters of the formula in which R1, R2, R3 and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms, Az represents an optionally substituted azolyl radical and Hal represents chlorine or bromine. 9. Process for the preparation of haloalkanecarboxylic acid azolylalkylesterh of the formula in which R1 R2 R3 and R4 R independently of one another represent hydrogen or alkyl having 1 to 4 carbon atoms, Az represents an optionally substituted azolyl radical and Hal represents chlorine or bromine, characterized in that halocarboxylic acid halides of the formula in which R1 and R2 have the meaning given above and Hal and Hal 'are chlorine or bromine, with hydroxyalkylazoles of the formula in which 4 R3, R4 and Az have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent. 10. Phenoxyphenoxyalkanecarboxylic acid azolylalkyl ester of the formula in which X1 and X2 independently represent hydrogen or halogen, R1, R2, R3 and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms and Az represents an optionally substituted azolyl radical. 11. Process for the preparation of phenoxyphenoxyalkanecarboxylic acid azolylalkyl esters of the formula in which X1 and X2 independently represent hydrogen or halogen, R1, R2, R3 and R4 independently represent hydrogen or alkyl having 1 to 4 carbon atoms and Az represents an optionally substituted azolyl radical, characterized in that phenoxyphenols of the formula in which X1 and X2 have the meaning given above, with haloalkanecarboxylic acid azolyl esters of the formula in which R1, R2, R3, R4, Az and Hal have the meaning given above, if appropriate reacted in the presence of an acid acceptor and if appropriate in the presence of a diluent.