DE3220523A1 - Phenoxyalkanecarboxylates, processes for their preparation, and their use as herbicides - Google Patents

Abstract

Novel phenoxyalkanecarboxylates of the formula <IMAGE> in which X<1> represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, X<2> represents hydrogen, fluorine, chlorine, bromine or iodine, R<1>, R<2>, R<3> R<4>, R<5> and R<6> independently of one another represent hydrogen or C1-C5-alkyl, Y represents oxygen, sulphur, a -NR group or a -COO group, R represents hydrogen or C1-C5-alkyl, m represents the numbers 1, 2 or 3, n represents the numbers 0 or 1 and p represents the numbers 1, 2 or 3, a plurality of processes for the preparation of the substances according to the invention, their use as herbicides, novel starting materials for the preparation of the compounds according to the invention, and the synthesis of these novel starting materials.

Description

Phenoxyalkanecarboxylic acid esters, process for their preparation

position and their use as herbicides The invention relates to new phenoxyalkanecarboxylic acid esters, several processes for their preparation as well as their use as herbicides.

It is already known that certain substituted diphenyl ethers have herbicidal properties (cf.

DE-OS 2 223 894). For example, the 2- / 4- (2,4-dichlorophenoxy) phenoxy7-propionic acid methyl ester can be used for weed control. The effect this stuff is good; however, the selectivity is not always sufficient.

There were now new phenoxy-alkanecarboxylic acid esters of the formula in which X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, X2 represents hydrogen, fluorine, chlorine, bromine or iodine, R1, R2, R3, R4, R5 and R6 independently of one another represent hydrogen or C1- C5-alkyl, Y stands for oxygen, sulfur, an -NR group or a -COO group, R stands for hydrogen or C1-C5-alkyl, m stands for the numbers 1, 2 or 3, n stands for the numbers 0 or 1 and p stands for the numbers 1, 2 or 3, found.

The compounds of the formula (I) can be in the syn or anti form are present. They are mainly obtained as a mixture of both forms. Those connections of formula (I), which contain one or more asymmetric carbon atoms, can occur in the form of racemates or various optical isomers. the The invention relates to both the steric and the optical isomers and their Mixtures.

It has also been found that new phenoxyalkanecarboxylic acid esters of the formula (I) are obtained if a) diphenyl ethers of the formula in which X1, X2, R5, R6 and p have the meaning given above, with compounds of the formula in which R11, R2, R3, R4, Y, m and n have the meaning given above and Hal stands for chlorine or bromine, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or b) phenoxyphenols of the formula in which x1 and x2 have the meaning given above and Z represents hydrogen, an alkali metal or an equivalent of an alkaline earth metal, with compounds of the formula in which R1, R21, R3, R, R5, R6, Y, m, n and p have the meaning given above and Hal1 represents chlorine or bromine, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, or c) phenoxy alkanecarboxylic acid esters of the formula in which X¹, X², R¹, R², R4, R5, R6, Y, m, n and p have the meaning given above, with alkylating agents of the formula R³'-Z1 (VI) in which R3 'is C1-C5-alkyl and Z¹ stands for chlorine, bromine, iodine, for a p-toluenesulfonyl group or for the grouping R7 O-SO2-O-, in which R7 stands for hydrogen or C1 -C5-alkyl, optionally using an acid acceptor and optionally in Reacts the presence of a diluent, or halides of the formula in which X¹, X², R¹, R², R3, R5, R6, Y, m and p are as defined above and Hal2 is chlorine or bromine, with compounds of the formula R4 -Q-Z2 (VIII) in which R4 is the has the meaning given above, Q is oxygen, sulfur or NR, where R has the meaning given above and z2 is hydrogen, an alkali metal or an equivalent of an alkaline earth metal, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, or e ) Nitriles of the formula in which X1, x2, R1, R2, R5, R6, m and p have the meaning given above, reacts with hydroxylamine or hydroxylamine hydrochloride or hydrobromide, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or f) compounds the formula in which X¹, X², R¹, R², R4, R5, R6, Y, m and p have the meaning given above and yl is oxygen or sulfur with hydroxylamine or hydroxylamine hydrochloride or hydrobromide, optionally in the presence of an acid acceptor and optionally reacted in the presence of a diluent, or g) carbonyl derivatives of the formula in which X², X², R1, R2, R5, R6, m and p are the above. have given meaning and R8 is C1-C4 alkyl, with hydroxylamine or hydroxylamine hydrochloride, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or h) trifluoromethylbenzenes of the formula in which X1 and x2 have the meaning given above and Hal3 represents chlorine or bromine, with compounds of the formula in which Y, R¹, R², R3, R4, R5, R6, m, n and p have the meaning given above and Z3 is hydrogen, an alkali metal or an equivalent of an alkaline earth metal, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or acid halides of the formula in which X¹, X2, R5, R6 and p are as defined above and Hal4 is chlorine or bromine, with compounds of the formula in which 1 R2, R3, R4, Y, m and n have the meaning given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent.

Finally, it was found that the new phenoxyalkanecarboxylic acid esters of formula (I) are characterized by excellent herbicidal properties.

Surprisingly, the phenoxyalkanecarboxylic acid esters according to the invention have of the formula (I) a significantly better herbicidal activity than the 2- / 4- (2,4-dichlorophenoxy) -phenoxy7-propionic acid methyl ester, which is a constitutionally similar, previously known Active ingredient is the same direction of action. The compounds according to the invention leave are also unexpectedly very good at defoliation of plants.

The substances according to the invention are generally defined by the formula (I). In this formula, X preferably represents hydrogen, fluorine, chlorine, nitro and Cyano, X² for hydrogen, fluorine or chlorine, R¹, R², R5 and R6 independently of one another for hydrogen, methyl or ethyl, R3 for hydrogen, methyl, Ethyl, n-propyl or iso-propyl, 4 R for hydrogen, methyl, ethyl, n-propyl or iso-propyl, Y represents oxygen, sulfur, an NR group or a -COO group, R represents hydrogen, methyl, ethyl, n-propyl or iso-propyl, m represents the number 1, n for the numbers 0 or 1 and p for the number 1.

The corresponding geometrical and optical properties are also preferred Isomers.

Particularly preferred optical isomers are the R and S enantiomers of the compounds of the formula in which Xl, X2, Rl, R2, R3, R4, Y, m and n have the preferred meanings given above and in which the carbon atom connected to the oxygen atom and marked by (*) in the side chain is a center of chirality. represents.

Xls are examples of the substances of the formula (I) according to the invention in detail the substances listed in the following table 1 in terms of formulas.

Table 1 X¹ X² R¹ R² R3 R4 R5 R6 Y n Cl Cl -CH3 H -CH3 H -CH3 H -0 Cl H -CH3 H -CH3 H -CH3 H -0 Cl H -CH3 H -CH3 -CH3 -CH3 H 0 1 Cl Cl -CH3 H -CH3 -CH3 -CH3 H 0 1 Cl HH H -CH3 -C2H5 -CH3 H 0 1 Cl H -CH3 H -C2H5 -CH3 -CH3 H 0 1 Cl H -CH3 H -C2H5 H -CH3 H - 0 Cl H -CH3 H -CH3 -C2H5 -CH3 H CO2 1 Cl Cl -CH3 H -C2H5 -C2H5 -CH3 H 0 1 Cl Cl -HH -CH3 -C2H5 -CH3 H CO2 1 Cl Cl -CH3 H - C2H5 H -CH3 H - 0 HH -CH3 H -CH3 -CH3 -CH3 HS 1 Cl H -CH3 H -CH3 -CH3 -CH3 HS 1 If you use 2- [4- (2,6-dichloro-4-trifluoromethyl- phenoxy) -phenoxy / -propionic acid and 2-bromo-1-methoximino-propane as starting materials, the course of process (a) according to the invention can be represented by the following equation: CH3 CH3 // NOCH3 F3C- Q C1 C 3 C 3 g OCH3 base H Cl Al CH3 O CH3 N-OCH3 F3C7-O \ -O-tO-CHC-O-CH 13th Cl If 4- (2-chloro-4-trifluoromethylphenoxy) phenol and 2- (1-methoxyimino) propyl 2-chloroacetate are used as starting materials, the course of process (b) according to the invention can be represented by the following equation : Cl 0 -0-Q-CH3 N-OCH FC + 1 1 // 3 -HCl -O-OH Cl-CH2-CO-CH-C H -HC1, Cl CH3 0 CH3 N-OCH3 1 CH, 1 O-CH - CO-CH - C 13th If 2- / 4- (2-chloro-4-trifluoromethylphenoxy) phenoxy / propionic acid (1-hydroximino-1-methoxy) prop-2-yl ester and dimethyl sulfate are used as starting materials, the course of the invention can Method (c) can be represented by the following equation: If 2-L4- (4-trifluoromethyl-phenoxy) -phenoxy7-acetic acid (1-chloro-1-methoximino) eth-2-yl ester and sodium ethoxide are used as starting materials, the course of process (d) according to the invention can be can be represented by the following equation: If 2- / 4- (2-chloro-4-trifluoromethyl-phenoxy) -phenoxy / -acetic acid cyanomethyl ester and hydroxylamine are used as starting materials, the course of process (e) according to the invention can be represented by the following equation: If the hydrochloride of 2-z4- (2-chloro-4-trifluoromethyl-phenoxy) -phenoxy7-acetic acid (1 -imido-1-ethoxy) -eth-2-yl ester and hydroxylamine are used as starting materials, the The course of process (f) according to the invention can be reproduced by the following equation: If 2- [4- (4-trifluoromethyl-phenoxy) -phenoxy] -propionic acid- (1-carbethoxy) -eth-1-yl-ester and hydroxylamine hydrochloride are used as starting materials, the course of the process according to the invention ( g) can be represented by the following equation: If 1,2,3-trichloro-5-trifluoromethylbenzene and 2- (4-hydroxyphenoxy) propionic acid (1-methoximino-1-ethoxy) prop2-yl ester are used as starting materials, the course of the invention can Method (h) can be represented by the following equation: Cl CH O CH3 0 CH N-OCH3 FC Q -C1 + HO- OO CH3 -> HCl F3C'-O-CH base C1 CH3 O CH3 N-OCH3 3 U O-CH - CO-CH - C / Cl OC 2H5 If 2- / 4- (4-trifluoromethylphenoxy) phenoxy7-propionic acid chloride and 1-methoximino-2-propanol are used as starting materials, the course of process (i) according to the invention can be represented by the following equation: The diphenyl ethers required as starting materials when carrying out process (a) according to the invention are defined by the formula (II). In this formula, X1, X2, R5, R6 and p 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 preferred for these radicals or for this index.

The compounds of the formula (II) are known or can be used conventional methods in a simple manner (compare e.g. DE-OS 2 311 638, GB-PS 2,058,055 and US-PS 4,031,131).

The further in process (a) according to the invention as starting materials The compounds required are defined by the formula (III). In this formula R1, R2, R3, R4, Y, m and n preferably have those meanings the already in connection with the description of the substances of the formula according to the invention (I) were preferably mentioned for these radicals or indices. Hal stands for chlorine or bromine.

The compounds of formula (III) are known (see e.g. US-PS 3 896 189, DE-OS 2 922 759, DE-OS 3 100 728 and DE-OS 1 937 454) or can produce in a simple manner using customary methods.

Compounds of formula (III) are thus obtained, for example, by - the underlying carbonyl compounds with hydroxylamine or hydroxylamine derivatives in the presence of a solvent such as an alcohol at temperatures between OOC and 100 "C, preferably between 0 ° C and 800C. The hydroxylamine or Hydroxylamine derivative is preferably in the form of a salt, in particular as the hydrochloride, optionally in the presence of an acid binder, such as, for example Sodium acetate, used.

In addition, compounds of the formula (III) can also be prepared by using compounds of the formula in which X¹, X², R³, R4, Y, m, n and p have the meanings given above, in the usual way chlorinated or brominated; or by adding alcohols of the formula in which R1, R2, R3, R4, Y, m and n have the meaning given above, reacted with halogenating agents, such as thionyl chloride or thionyl bromide, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.

When carrying out process (a) according to the invention, works is preferably carried out in the presence of an acid acceptor. As such, all can usual Find acid binders use. Alkali hydroxides are preferred, such as sodium and potassium hydroxide, alkali carbonates and alcoholates, such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, further aliphatic, aromatic or heterocyclic amines, for example triethylamine, Trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, diazabicyclooctane, 1 , 5-diazabicyclo / 4,3,07nen-5 and 1,8-diazabicyclo / 5,4,07undecene-7.

When carrying out the inventive Process (a) practically all inert organic solvents can be used. Preferably Aliphatic and aromatic, optionally halogenated hydrocarbons are suitable, 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 ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, also ketones, such as acetone, Methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl esters, furthermore nitriles, such as acetonitrile and propionitrile, above in addition to amides, such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, as well as strongly polar solvents such as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid triamide.

The reaction temperatures can when carrying out the invention Process (a) can be varied within a relatively wide range. In general one works at temperatures between -200C and + 1500C, preferably between OOC and + 1200C.

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

When carrying out process (a) according to the invention, the Starting materials of the formulas (II) and (III) generally in approximately equimolar amounts used.

An excess of one or the other component is possible 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 carried out by customary methods.

Some of the new compounds are in the form of oils which sometimes not allowed to distill undecomposed, but by so-called "Andestilieren", i.e.

increased to moderate by prolonged heating under reduced pressure Temperature freed from the last volatile components and cleaned in this way can be.

The refractive index is used to characterize the new substances. If the new products are obtained in solid form, they can be recrystallized getting cleaned. The melting point is then used for characterization.

When carrying out process (b) according to the invention as Phenoxyphenols required starting materials are 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. Z preferably represents hydrogen, sodium, potassium or for one equivalent of a calcium ion.

The phenoxyphenols of formula (IV) are known (see e.g. U.S. Patent 3,928,416).

Those also to be used as starting materials in process (b) Compounds are defined by the formula (V). In this formula, R1, R2, R3, R4, R5, R6, Y, m, n and p preferably have those meanings which are already in the Preferably in connection with the description of the substances of the formula (I) according to the invention for these residues or indices were mentioned. Hal¹ stands for chlorine or bromine.

The compounds of the formula (V) are new. They can be prepared by α) carbonyl compounds of the formula in which R1 R2 R4 R5 R6 Y, Hal1 m, n and p have the meaning given above, with hydroxylamine or with hydroxylamine derivatives in the presence of a diluent, such as an alcohol, and optionally in the presence of an acid binder, such as, for example Sodium acetate, at temperatures between OOC and 100 ° C., preferably between 0 ° C. and 80 ° C., the hydroxylamine or the hydroxylamine derivative preferably being used in the form of a salt, in particular as the hydrochloride, or that B) compounds of the formula in which R1, R2, R3, R4, R5, R61, Y, in, n and p have the meanings given above, chlorinated or brominated in the customary manner, or alcohols of the formula in which R¹, R², R3, R4, R5, R6, Y, m, n and p have the meaning given above, with thionyl chloride or thionyl bromide, optionally in the presence of an acid acceptor and optionally in the presence of a diluent at temperatures between 0 ° C and 80 ° C converts, or alcohols of the formula in which R, R², R³, R4 ', Y, m and n have the meanings given above, with carboxylic acid halides of the formula in which R5, R6, Hal and p have the meaning given above and Hal5 is chlorine or bromine, optionally in the presence of a diluent such as tetrahydrofuran or toluene, and optionally in the presence of an acid acceptor such as

Pyridine or potassium carbonate, at temperatures between -200C and + 1200C, preferably between OOC and 800C1.

Acid acceptors which can be used in process (b) according to the invention all common acid binders can be used.

All those acid binders which are in connection with with the description of the process (a) according to the invention.

When carrying out the inventive Process (b) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (b) can be varied within a relatively wide range. In general one works at temperatures between -200C and + 1500C, preferably between OOC and + 1200C.

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

When carrying out process (b) according to the invention, the Starting materials of the formulas (IV) and (V) generally in approximately equimolar amounts used. An excess of one or the other component is possible.

The reaction is generally carried out in a suitable diluent carried out in the presence of an acid acceptor, and the reaction mixture becomes several Stirred for hours at the required temperature. The work-up and the cleaning the substances are carried out according to customary methods.

When carrying out process (c) according to the invention as Phenoxy-alkanecarboxylic acid esters required starting materials are represented by the formula (Ia) Are defined. In this formula, X1, X2, R1, R2, R4, R5, R6, Y, in, n and p preferably have those meanings which are broadly in connection with the description of the invention Substances of the formula - (I) preferably for these residues or

Indices were named The compounds of the formula (Ia) are new. However, they can be produced by process (a) according to the invention.

The further in process (c) according to the invention as starting materials alkylating agents to be used are defined by the formula (VI). In this Formula R3 preferably represents methyl, ethyl, n-propyl and iso-propyl.

stands for chlorine, bromine, iodine, a p-toluenesulfonyl group or for the grouping R70-SO.-0-, in which R7 is preferably hydrogen, methyl, ethyl, n-propyl or iso-propyl.

The compounds of the formula (VI) are generally known compounds of organic chemistry.

Acid acceptors which can be used in process (c) according to the invention all common acid binders can be used. Preferably all are eligible those acid binders, which in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (c) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (c) can be varied within a relatively wide range. In general one works at temperatures between -20 and + 120 ° C, preferably between -10 and + 1000C.

Process (c) according to the invention is generally carried out under normal pressure executed.

When carrying out process (c) according to the invention, the Starting materials of the formulas (Ia) and (VI) generally in approximately equimolar amounts used. An excess of one or the other component is possible.

The reaction is generally carried out in a suitable diluent carried out in the presence of an acid acceptor, and the reaction mixture becomes several Stirred for hours at the required temperature. The work-up and the cleaning the substances are carried out according to customary methods.

When carrying out process (d) according to the invention as Starting materials required halides are defined by the formula (VII). In of this formula, X1 x, R1, R2, R31, R5r, R6, m and p preferably have those meanings which already in connection with the description of the substances according to the invention of Formula (I) have preferably been mentioned for these radicals or indices.

Hal stands for chlorine or bromine.

The halides of the formula (VII) are new. They can be prepared by taking hydroxamic acid derivatives of the formula in which X¹, X², R¹, R², R3, R5, R6, Y, m, n and p have the meanings given above, or their tautomeric compounds or aldoximes of the formula in which X¹, X², R¹, R², R5, R6, m and p have the meanings given above, with chlorinating or brominating agents, such as the by-.

play phosphorus pentachloride, phosphorus tribromide, chlorine or bromine, if appropriate in the presence of an acid acceptor, such as pyridine, at temperatures between -400C and + 600C converts (see. Houben-Weyl, "Methods of Organic Chemistry", Volume VIII, pages 691-692).

The compounds of the formulas (Id) and (Ie) are also new; she however, can be produced in a simple manner by process (a) according to the invention.

Those still to be used as starting materials in process (d) Compounds are defined by the formula (VIII). In this formula, R4 preferably has those meanings already in connection with the description of the invention Substances of the formula (I) were mentioned as preferred for this radical. Z² is preferably for hydrogen, sodium or potassium or for one equivalent of a calcium ion. Q preferably represents oxygen, sulfur or the NR group, in which R is preferably represents hydrogen, methyl, ethyl, n-propyl or iso-propyl. The connections of formula (VIII) are known.

Acid acceptors which can be used in process (d) according to the invention all common acid binders can be used. Preferably -all come into question those acid binders, which in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (d) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (d) can be varied within a relatively wide range. In general one works at temperatures between -20 and + 1500C, preferably between -10 and + 1200C.

Process (d) according to the invention is generally carried out under normal pressure executed.

When carrying out process (d) according to the invention, are Starting materials of the formulas (VII) and (VIII) generally in approximately equimolar amounts used. An excess of one or the other component is possible.

The reaction is generally carried out in a suitable diluent carried out in the presence of an acid acceptor, and the reaction mixture becomes several Stirred for hours at the required temperature. The work-up and the cleaning the substances are carried out according to customary methods.

When carrying out the process (e) according to the invention as Nitriles required starting materials are defined by the formula (IX). In this Formula X1, X2 R1, R2, R5 R6, m and p preferably have those meanings which already in connection with the description of the substances according to the invention of Formula (I) have preferably been mentioned for these radicals or indices.

Some of the compounds of the formula (IX) are known (cf. DE-OS 2 613 697). You can get by making connections of the formula (II) with the corresponding halonitriles in the presence of an inert organic Solvent, such as acetonitrile, and optionally in the presence of an acid binder, such as potassium carbonate, optionally in the presence of a catalyst, e.g. Sodium iodide, at temperatures between 0 and 100 ° C.

Acid acceptors which can be used in the process according to the invention (e) all common acid binders can be used. Preferably all are eligible those acid binders, which in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (e) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (e) can be varied within a larger range. In general one works at temperatures between -20 and + 1200C, preferably between -10 and + 1000C.

Process (e) according to the invention is generally carried out at normal pressure executed.

When carrying out process (e) according to the invention, one uses preferably 1 to 2 moles of hydroxylamine per mole of the compounds of the formula (IX) and hydroxylamine hydrochloride or hydrobromide, respectively. Implementation is in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is kept at the required temperature for several hours touched. The substances are worked up and purified in accordance with the usual methods Methods.

When carrying out process (f) according to the invention as The compounds required for starting materials are defined by the formula (X). In this Formula X1, X2, R1, R2, R4, R5, R6, m and p preferably have those meanings which already in connection with the description of the substances according to the invention of Formula (I) have preferably been mentioned for these radicals or indices. y1 stands for Oxygen or sulfur.

The compounds of the formula (X) are new. They can be made by taking nitriles of the formula in which X1, X2 1 R2, R5, R6, m and p have the meaning given above, with compounds of the formula R4 - y1 - H (XXI) in which R4 and y1 have the meaning given above, in the presence of hydrogen chloride and in The presence of a solvent, such as toluene, reacts at temperatures between -100C and 300C (compare e.g.

DE-OS 2 746 057 and Ber. German Chem. Ges. 16, 356 (-1883)) The compounds of the formula (XXI) are generally known compounds of organic chemistry.

Acid acceptors which can be used in process (f) according to the invention all common acid binders can be used. Preferably all are eligible those acid binders, which in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (f) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (f) can be varied within a relatively wide range. In general one works at temperatures between -20 and + 500C, preferably between -10 and + 300C.

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

When carrying out process (f) according to the invention, one uses preferably 1 to 2 moles of hydroxylamine for 1 mole of the compounds of the formula (X) or hydroxylamine hydrochloride or hydroxylamine hydrobromide. The implementation will generally in the presence of a diluent and in the presence of an acid acceptor carried out, and the reaction mixture is several hours at the required Temperature stirred. The work-up and purification of the substances take place after usual methods.

Those required as starting materials in process (g) according to the invention Carbonyl derivatives are defined by the formula (XI). In this formula, X11 X2, R11, R2, R5, R6r m and p preferably have those meanings which are already in the Preferably in connection with the description of the substances of the formula (I) according to the invention for these residues or indices were mentioned. R8 preferably represents methyl or Ethyl.

The carbonyl derivatives of the formula (XI) are known or can be by conventional methods in a simple manner manufacture (compare e.g. DE-AS 2 304 006 Gb-Pb 2 658 655 and EP-OS 28 277).

Acid acceptors which can be used in the process according to the invention (g) all common acid binders can be used. Preferably all are eligible those acid binders, which in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (g) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (g) can be varied within a relatively wide range. In general one works at temperatures between -20 and + 120 ° C, preferably between -10 and + 800C.

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

When carrying out process (g) according to the invention, one uses preferably 1 to 2 moles of hydroxylamine for 1 mole of carbonyl derivative of the formula (XI) or hydroxylamine hydrochloride. The reaction is generally carried out in a suitable Diluent in the presence of a Acid acceptor carried out, and the reaction mixture is kept at the required temperature for several hours touched. The substances are worked up and purified in accordance with the usual methods Methods.

The trifluoromethylbenzenes required in process (h) according to the invention are defined by the formula (XII).

In this formula, X1 and X2 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. Hal stands for chlorine or Bromine.

The trifluoromethylbenzenes of the formula (XII) are generally known Compounds of organic chemistry.

Those still required as starting materials for process (h) Compounds are defined by formula (XIII). In this formula, R1, R2, R3, R, R5, R6, Y, m, n and p preferably have those meanings which are already in the Preferably in connection with the description of the substances of the formula (I) according to the invention for 3 these residues or indices were mentioned. Z3 preferably represents hydrogen, Sodium, potassium or for an equivalent of a calcium ion.

Some of the compounds of the formula (XIII) are known. You let can be produced in a simple manner analogously to process (a) according to the invention.

Acid acceptors which can be used in the process according to the invention (h) all common acid binders can be used. Preferably all are eligible those acid binders which, in connection with the description of the invention Procedure (a).

When carrying out the inventive Process (h) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (h) can be varied within a relatively wide range. In general one works at temperatures between 0 ° C and + 1800C, preferably between 600 and + 1400C.

Process (h) according to the invention is generally carried out under normal pressure executed.

When carrying out process (h) according to the invention, the Starting materials of the formulas (XII) and (XIII) generally in approximately equimolar amounts used. An excess of one or the other component is possible. The implementation is generally in a suitable diluent in the presence of an acid acceptor carried out, and the reaction mixture will take several hours stirred at the required temperature. The processing and purification of the substances take place according to the usual methods.

Those required as starting materials for process (i) according to the invention Acid halides are defined by the formula (XIV). In this formula, X1, X2, R5, R6 and p 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 residues or this index were named. Hal4 stands for chlorine or bromine.

The compounds of the formula (XIV) are known (compare e.g. DE-OS 2 906 087) or can be easily produced using the processes mentioned there.

Those still required as starting materials for process (i) Compounds are defined by the formula (XV). In this formula, R1, R2, R3, R4, Y, 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 residues or indices were called.

The compounds of the formula (XV) are already known (cf. DE-OS 3 100 728).

: Acid acceptors can be used in the methods according to the invention. l j chen acid binders can be used. Preferably all of those are eligible Acid binders in connection with the description of the method according to the invention (a) were named.

When carrying out the inventive Process (i) practically all inert organic solvents can be used. Preferably those diluents that come into consideration in connection with the description of the process (a) according to the invention were mentioned.

The reaction temperatures can when carrying out the invention Process (i) can be varied within a relatively wide range. In general one works at temperatures between -40 and + 1600C, preferably between 0 and + 1100C.

Process (i) according to the invention is generally carried out under normal pressure executed.

When carrying out process (i) according to the invention, the Starting materials of the formulas (XIV) and (XV) generally in approximately equimolar amounts used. An excess of one or the other component is possible. 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 stirs. The processing and purification of the substances take place according to the usual methods.

The active ingredients according to the invention can be used as defoliants, desiccants, Haulm killers and especially used as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention as total or selective The effect of herbicides 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, Setarial Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, t ropyron, Cynodon, loonochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, apera.

Monocot cultures of the genera: Oryza, Zea Triticum, Hordeum, Avena, Secale, Sorghum, Panicwm, 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 vegetation. Likewise, the compounds can be used for weed control in permanent crops, e.g. forest, ornamental wood, wine, citrus, nut, banana, coffee, Tea, rubber, olive 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 major crops, such as beets and Soybeans, suitable. In addition, the active ingredients according to the invention can be very effective use well for defoliation and to dry out the leaves of cotton. Farther the active compounds according to the invention also have an insecticidal activity.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granulates, suspension-emulsion concentrates, impregnated with active ingredients 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 carriers, optionally with the use of surface-active agents, that is, emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents, for example, can also be used can be used as co-solvents. The liquid solvents used are essentially in question: aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, 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.

Possible solid carriers are: e.g. ammonium salts and natural ones Ground rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as highly dispersed silica, Alumina and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn on the cob and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: 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.

The formulations generally contain between 0.1 and 95 percent 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.

Known herbicides such as e.g.

1-Amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -dione or N- (2-benzthiazolyl) -N, N'-dimethyl urea for weed control in cereals; 4-Amino-3-methyl-6-phenyl-1, 2,4-triazin-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-1, 2,4-triazin-5 (4H) -one for weed control in soybeans, in question. Surprisingly, some mixtures also show synergistic properties Effect.

Also a mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible.

The active ingredients can be used as such, in the form of their formulations or the resulting from further dilution @@@@@@@@ @@@@@@@@@@@@@@@@ such as @@@@@@@@@@@@@ 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 preferably used after emergence of the plants, i.e. in the postemergence process, performed. They can also be incorporated into the soil before sowing.

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 can be seen from the following examples.

Preparation examples Example 1 (Method i) * A-Form To a solution of 2.7 g (0.026 mol) of 1-methoximino-2-propanol in 50 ml of dichloromethane and 2.3 g (0.029 mol) of pyridine is added dropwise 8.4 at 20 to 30 ° C g (0.022 mol) of 2- [4- (2-chloro-4-trifluoromethyl-phenoxy) -phenoxy] -propionic acid chloride and heated to 40 ° C. for 2 hours. It is then taken up in 200 ml of dichloromethane, washed twice in succession with aqueous sodium hydrogen carbonate solution and water, dried over sodium sulfate and concentrated. 6.7 g (65% of theory) of 2- / 4- (2-chloro-4-trifluoromethylphenoxy) phenoxy / propionic acid 2- (l-methoximino) propyl ester are obtained as a pale oil with a refractive index nD : 1.5139.

Preliminary products 45 g (0.45 mol) of 1-methoximino-2-oxo-propane are cooled to OOC. A solution of 4.5 g (0.12 mol) of sodium boronate in 20 ml of water is slowly added dropwise so that the temperature does not exceed 30 ° -400 ° C. (ice cooling). After stirring for two hours, the aqueous phase is separated off and extracted several times with dichloromethane. The combined organic phases are dried over sodium sulfate and distilled in vacuo. 35.7 g (80% of theory) of 1-methoximino-2-propanol with a boiling point of 600 ° C./20 mm Hg are obtained.

131 g (1.5 mol) of l-hydroximino-2-oxo-propane are dissolved in 150 ml of water suspended. A solution of 63 g (1.575 mol) of sodium hydroxide is added dropwise at OOC in 100 ml of water, and then 208 g (1.65 mol) of dimethyl sulfate are added dropwise. After stirring for several hours, the organic phase is separated off and the aqueous phase Phase is extracted several times with dichloromethane. The combined organic phases are dried over sodium sulfate and the solvent is at normal pressure removed. The product is purified by distillation.

99.5 g (65% of theory) of 1-methoximino-2-oxo-propane are obtained Boiling point 230C / 19 mm Hg.

Using the method described in the previous example or those in the following table are also obtained by other processes according to the invention 2 compounds listed by the formula.

Table 2 Example X 1 X 2 R 1 R 2 R 3 R4 R5 R6 m Y np Melting point [° C] No. or refractive index [nD-20] 2 HH CH3 H CH3 H CH3 H 1-0 1 nD22 = 1.5090 3 Cl Cl CH3 H CH3 C2H5 CH3 H 1 0 1 1 1.5184 4 Cl Cl CH3 H C2H5 CH3 CH3 H 1 0 1 1 1.5170 5 Cl Cl CH3 H C2H5 H CH3 H 1 - 0 1 1.5191 6 HH CH3 H CH3 C2H5 CH3 H 1 0 1 1 1.5019 7 HH CH3 H C2H5 C2H5 CH3 H 1 0 1 1 1.5030 8 HH CH3 H C2H5 H CH3 H 1 - 0 1 1.5005 9 Cl H CH3 H CH3 C2H5 CH3 H 1 0 1 1 1.5108 10 Cl H CH3 H C2H5 H CH3 H 1 - 0 1 1.5102 11 HH CH3 H CH3 H CH3 H 1 - 0 1 1.5049 (A-Form *) * Forms A and B are the two possible steric ones Isomers.

Example 12 (Method a) A mixture of 5 g (0.0125 mol) 2- / 4- (2,6-dichloro-4-trifluoromethyl-phenoxy) -phenoxy] -propionic acid, 2 g 1,8-Diaza'Dicyclo / - 5.4.07undecene-7 and 3.4 g (0.015 mol) of ethyl 3-bromo-2-methoximino-propionate in 50 ml of toluene are stirred for 5 hours at 45 ° C. with exclusion of moisture. After the reaction mixture has stood at room temperature for 16 hours, the reaction mixture is filtered. The filtrate is drawn up on 30 g of silica gel and eluted with a mixture of cyclohexane: acetone = 1: 1. Evaporation of the main fraction gives 5 g (73% of theory) of 2- / 4- (2,6-dichloro-4-trifluoromethylphenoxy) phenoxy / propionic acid (2-methoximino-2-carbethoxy) ethyl ester in the form of a light oil with a refractive index of nD = 1.5185.

Pre-product: In a mixture of 613.5 g (8.58 mol) of O-'4ethyl-hydroxylamine hydrochloride in 1430 ml of chloroform and 1430 ml of water, 1394 g (7.15 mol) of ethyl pyruvate are added dropwise at room temperature with stirring. After stirring for 4 hours, the organic phase is separated off, washed twice with water, dried over sodium sulfate and then concentrated.

By distilling the remaining residue, 1338 g are obtained (83.6% of theory) of 3-bromo-2-methoximinopropionic acid ethyl ester in the form of a colorless, tear-irritating oil.

Bp. 83 - 880C / 1.5 mbar.

Example 13 Following the method described in Example 12, the compound of the formula is also obtained 20 nD = 1.5081 In the following examples, the compound given below is used as a comparison substance: 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid methyl ester (DE-OS 2 223 894).

Example A Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

With the active ingredient preparation you spray test plants, which one Height of 5-15 cm so that the particular amounts of active ingredient desired per unit area be applied. The concentration of the spray liquor is chosen so that in 2000 1 water / ha, the particular amounts of active compound desired are applied. After three For weeks, the degree of damage to the plants is rated in% damage in comparison to develop the untreated control. It means: 0% = no effect (like untreated control) 100% = total destruction Active ingredients (6), (8), (13), (9) and (10) a better selective herbicidal effectiveness than the comparative substance (A).

Example B Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amount of solvent, add the specified amount of emulsifier and dilute the concentrate 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 one The active ingredients (6), (8), (13), (9) and (10) according to the invention show a very test good herbicidal effectiveness.

Example C Defoliation and drying 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 have a strong to very strong effectiveness.

Claims (12)

Claims (1) / Phenoxyalkanecarboxylic acid esters of the formula in which xl represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, X² represents hydrogen, fluorine, chlorine, bromine or iodine, R1, R2, R3, R41, R5 and R independently of one another represent hydrogen or C1-C5 -Alkyl, Y stands for oxygen, sulfur, an -NR group or a -COO group, R stands for hydrogen or C1-C5-alkyl, m stands for the numbers 1, 2 or 3, n stands for the numbers 0 or 1 and p stands for the numbers 1, 2 or 3. 2) Phenoxyalkanecarboxylic acid esters of the formula (I) in which xl represents hydrogen, fluorine, chlorine, nitro or cyano, x2 represents hydrogen, fluorine or chlorine, R1, R2 5 and R6 independently of one another represent hydrogen, methyl or ethyl, R3 represents hydrogen, methyl, ethyl, n-propyl or iso-propyl, R4 represents hydrogen, methyl, ethyl, n-propyl or iso-propyl, Y represents oxygen, Sulfur, an NR group or a -COO group, for hydrogen, methyl, ethyl, n-propyl or iso-propyl, m stands for the number 1, n for the numbers 0 or 1 stands and p stands for the number 1. 3) R or S enantiomers of compounds of the formula in which X1 represents hydrogen, fluorine, chlorine, nitro or cyano, X² represents hydrogen, fluorine or chlorine, R¹ and R² independently represent hydrogen, methyl or ethyl, R3 represents hydrogen, methyl, ethyl, n-propyl or iso -Propyl, R4 is hydrogen, methyl, ethyl, n-propyl or iso-propyl, Y is oxygen, sulfur, an NR group or a -COO group, R is hydrogen, methyl, ethyl, n-propyl or iso-propyl, m stands for the number 1 and n stands for the numbers 0 or 1. 4) Process for the preparation of phenoxyalkanecarboxylic acid esters of the formula in which X represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, x2 represents hydrogen, fluorine, chlorine, bromine or iodine, R1, R2, R3, R4, R5 and R6 independently of one another represent hydrogen or C1- C5-alkyl, Y stands for oxygen, sulfur, an -NR- group or a -COO- group, R stands for hydrogen or C1-C5-alkyl, m stands for the numbers 1, 2 or 3, n stands for the numbers 0 or 1 and p stands for the numbers 1, 2 or 3, characterized in that a) diphenyl ethers of the formula in which X1, X2, R5, R6 and p have the meaning given above, with compounds of the formula in which R1, R2, R3, d, Y, m and n have the meaning given above and Hal represents chlorine or bromine, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or b) phenoxyphenols of the formula X¹ and X² are as defined above and Z is hydrogen, an alkali metal or an equivalent of an alkaline earth metal, with compounds of the formula in which 1 R2, R31, R4, R5, R6, Y, m, n and p have the meaning given above and Hal1 is chlorine or bromine, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or c) phenoxyalkanecarboxylic acid -ester of the formula in which X¹, X², R¹, R², R4, R5, R6, Y, m, n and p have the meaning given above, -with alkylating agents of the formula R3 '~ 1 (VI) in which R³' represents C1-C5- Alkyl and Z¹ for chlorine, bromine, iodine for a p-toluenesulfonyl group or for the grouping R7 O-SO2-O, in which R7 is hydrogen or C1-C5-alkyl, optionally using an acid acceptor and optionally in the presence of a diluent, or d) halides of the formula in which X1, X², R¹, R², R³, R5, R6, m and p are as defined above and Hal2 is chlorine or bromine, with compounds of the formula R4 - Q - Z² (VIII) in which R4 is as indicated above Q is oxygen, sulfur or an NR group, where R has the meaning given above and Z2 is hydrogen, an alkali metal or an equivalent of an alkaline earth metal, optionally reacted in the presence of an acid acceptor and optionally in the presence of a diluent, or e) nitriles of the formula in which X1, X2, R1, R27, R5, R6, m and p have the meaning given above, with hydroxylamine or hydroxylamine hydrochloride if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or f) compounds of the formula in which X¹, X², R¹, R², R4, R5, R6, m and p have the meaning given above and yl is oxygen or sulfur, with hydroxylamine or hydroxylamine hydrochloride or hydrobromide, optionally in the presence of an acid acceptor and optionally in the presence a diluent, or g) carbonyl derivatives of the formula in which X¹, x2 R1 R2, R5, R6, m and p have the meaning given above and R8 stands for C1-C4-alkyl, with hydroxylamine or hydroxylamine hydrochloride, optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or h) trifluoromethylbenzenes of the formula in which X¹ and X² are as defined above and Hal³ is chlorine or bromine, with compounds of the formula in which Y, R¹, R2, R3, R4, R5, R6, m, n and p have the meaning given above and Z3 is hydrogen, an alkali metal or an equivalent of an alkaline earth metal, optionally in the presence of an acid acceptor and optionally in the presence of one Reacts diluent, or i) acid halides of the formula in which X1, X2, R5, R6 and p have the meaning given above and Hal4 is chlorine or bromine, with compounds of the formula in which R¹, R², R³, R4, Y, m and n have the meanings given above, optionally in the presence of an acid acceptor and optionally in the presence of a diluent. 5) Herbicidal agents, characterized by a content of at least a phenoxyalkanecarboxylic acid ester of the formula (I). 6) method for combating weeds, characterized in that that one phenoxy-alkanecarboxylic acid ester of the formula (I) on the weeds and / or their habitat. 7) Use of phenoxy-alkanecarboxylic acid esters of the formula (I) for Control of weeds. 8) Process for the preparation of herbicidal agents, characterized in that that one phenoxyalkanecarboxylic acid ester of the formula (I) with extenders and / or mixed surfactants. 9) halides of the formula in which xl represents hydrogen, fluorine1 chlorine, bromine, iodine, nitro or cyano, X² represents hydrogen, fluorine, chlorine, bromine or iodine, R¹, R², R³, R5 and R6 independently of one another represent hydrogen or C1-C5-alkyl stand, m stands for the numbers 1, 2 or 3, p stands for the numbers 1, 2 or 3 and Hal2 stands for chlorine or bromine. 10) Process for the preparation of halides of the formula in which xl represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, x2 represents hydrogen, fluorine, chlorine, bromine or iodine, R¹, R2, R3, R5 and R4 independently of one another represent hydrogen or C C1-C5 -Alkyl, m stands for the numbers 1, 2 or 3, p stands for the numbers 1, 2 or 3 and Hal2 stands for chlorine or bromine, characterized in that hydroxamic acid derivatives of the formula in which X1, X2, R, R², R3, R51, R6, m and p have the meaning given above, or their tautomeric compounds or aldoximes of the formula in which X11, X2, R1, R2, R5, R6, m and p are as defined above, reacted with chlorinating or brominating agents, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent. 5 10 15 11) compounds of the formula in which xl represents hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, X represents hydrogen, fluorine, chlorine, bromine or iodine, R11, R2, R4, R5 and R6 independently of one another represent hydrogen or C1-C5-alkyl stand, m stands for the numbers 1, 2 or 3, p stands for the numbers 1, 2 or 3 and 1 stands for oxygen or sulfur. 12) Process for the preparation of compounds of the formula in which x1 stands for hydrogen, fluorine, chlorine, bromine, iodine, nitro or cyano, x2 stands for hydrogen, fluorine, chlorine, bromine or iodine, R¹, R², R4, R5 and R6 independently of one another are hydrogen or C1-C5- Are alkyl, m stands for the numbers 1, 2 or 3, p stands for the numbers 1, 2 or 3 and y1 stands for oxygen or sulfur, characterized in that one in which X1, X2, R1, R2, R5, R6, m and p have the meaning given above1 with compounds of the formula R4 - Y1 - H (XXI) in which R4 and yl have the meaning given above, in the presence of hydrogen chloride and optionally reacted in the presence of a diluent.