EP0501986A1

EP0501986A1 - Isoxazolines, method of preparation thereof, and their use as plant-protection agents

Info

Publication number: EP0501986A1
Application number: EP19900916475
Authority: EP
Inventors: Heinz Josef LÖHER; Wilfried Schwab; Klaus Bauer; Hermann Bieringer
Original assignee: Hoechst AG; Hoechst Schering Agrevo GmbH
Current assignee: Bayer CropScience AG
Priority date: 1989-11-25
Filing date: 1990-11-17
Publication date: 1992-09-09
Also published as: CN1052308A; IL96458A0; DE3939010A1; NZ236199A; HU9201711D0; US5314863A; CA2069406A1; AU6716090A; AU654119B2; IL96458A; HUT61649A; ZA909410B; WO1991008202A1

Abstract

Les composés de formule (I), où Z, X et n sont définis comme dans la revendication 1, peuvent être employés comme antidotes de la phytotoxicité de nombreux herbicides sur les plantes cultivées, sans que le pouvoir herbicide contre les plantes nuisibles soit affecté.The compounds of formula (I), where Z, X and n are defined as in claim 1, can be used as antidotes for the phytotoxicity of numerous herbicides on cultivated plants, without the herbicidal power against harmful plants being affected.

Description

description

Isoxazolines, process for their preparation and their

Use as a crop protection agent

The invention relates to safeners or antidotes, which in

Combination with herbicides can reduce the phytotoxicity of herbicides in crops.

The invention relates to plant-protecting isoxazolines of the general formula (I) or their salts

(I)

wherein

Z independently of one another halogen, nitro, cyano or

Alkyl, alkoxy, alkylthio or cycloalkyl, the last four radicals mentioned unsubstituted or one or more times by alkoxy, hydroxy or halogen

are substituted, or furthermore amino, mono- or

Dialkylamino, phenyl or phenoxy, where phenyl and phenoxy are independently unsubstituted or substituted one or more times by halogen or haloalkyl, or two adjacent substituents 2 together for a divalent group of the formula -OCH ₂ O-, -S-CH ₂ -O - or -S-CH ₂ -S-, which is unsubstituted or substituted by alkyl, n is an integer from 0 to 5,

X is hydroxy or alkoxy, alkenyloxy, alkynyloxy, alkylthio or cycloalkoxy, the five latter radicals are unsubstituted or substituted one or more times by radicals from the group alkoxy, alkylthio, mono- and dialkylamino, phenyl, substituted phenyl, cyano and halogen, or

furthermore phenoxy or substituted phenoxy, or furthermore trialkylsilylmethoxy, a radical of the formula

in which each R is hydrogen or alkyl, Z ^1, independently of 2, has the meanings given above for 2 and n ^{1 is} an integer from 0 to 5, or furthermore amino, mono- or dialkylamino, cycloalkylamino, hydrazino, alkyl- or dialkylhydrazino, Pyridino, morpholino, dimethylmorpholino, a radical of the formula

wherein R ¹ and R ² independently of one another are alkyl radicals or R ¹ and R ² together with them

linking carbon atom form a cycloalkyl radical, or further a radical of the formula where R ³ and R ^{4 are} independently hydrogen or alkyl,

mean. In formula (I) alkyl, alkoxy, haloalkyl,

Alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in each case

straight chain or branched. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean methyl, ethyl, n- and i-propyl, n-, i-, t- and

2-butyl, the isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl radicals and the

longer chain fatty alkyl residues with up to 24 C atoms;

C ₁ -C ₁₂ alkyl radicals are preferred. Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, preferably (C ₂ -C ₁₂ ) alkenyl and alkynyl radicals. Halogen means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

If X = OH, the compounds of the formula (I) can form salts. The salts which can be used in agriculture can be used according to the invention. As such come

for example metal salts such as alkali or alkaline earth metal salts, in particular sodium or potassium salts, ammonium salts or substituted ammonium salts, which are substituted 1 to 4 times by alkyl and / or alkanol radicals with preferably up to 4 carbon atoms.

Formula (I) also covers all stereoisomers and their mixtures, in particular also pure enantiomers and their

Mixtures (e.g. racemates). Stereoisomers can occur especially when asymmetric or suitable

substituted double bonds are present in the formula (I). An asymmetric carbon atom is the carbon atom bound to the oxygen atom in the isoxazoline ring.

Of particular interest are inventive

plant-protecting compounds of the formula (I) in which

2 independently of one another halogen, nitro, cyano, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, the alkyl, alkoxy and alkylthio groups being unsubstituted or mono- or are substituted several times by halogen atoms, in particular fluorine or chlorine, (C ₃ -C ₆ ) cycloalkyl which is unsubstituted or substituted by (C ₁ -C ₄ ) alkyl, amino, (C ₁ -C ₄ ) alkylamino, di- ( C ₁ -C ₄ ) alkylamino,

Hydroxymethyl, (C ₁ -C ₄ ) alkoxy-methyl, phenyl or phenoxy, where phenyl and phenoxy are unsubstituted or one or more times by halogen or simply by trifluoromethyl or by one or more halogen atoms and one

Trifluormethyl is substituted, or two adjacent substituents Z for the divalent group -O-CH ₂ -O-,

-S-CH ₂ -O- or -S-CH ₂ -S- stand and

n 0, 1, 2 or 3

mean. Of particular interest are agents according to the invention with compounds of the formula (I) in which

X hydroxy, -OCH ₂ Si (CH ₃ ) ₃ , (C ₃ -C ₆ ) cycloalkoxy,

Phenyl (C ₁ -C ₆ ) alkoxy, phenoxy, (C ₂ -C ₆ ) alkenyloxy,

(C ₂ -C ₆ ) alkynyloxy, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkylthio, the alkoxy or alkylthio group being unsubstituted or mono- or disubstituted by (C ₁ -C ₂ ) alkoxy, mono- or di- (C ₁ -C ₆ ) alkylamino, (C ₁ -C ₂ ) alkylthio, cyano or substituted one or more times by halogen,

a rest of the formula

wherein each R is hydrogen or (C ₁ -C ₄ ) alkyl, Z ^{1 has} the meaning given above for Z and n ^{1 is} 0, 1, 2 or 3, or

furthermore amino, mono- or di- (C ₁ -C ₄ ) alkylamino, (C ₅ -C ₆ ) - cycloalkylamino, hydrazino, piperidino, morpholino or 2,6-dimethylmorpholino, a radical of the formula

wherein

R ¹ and R ² independently of one another are (C ₁ -C ₄ ) alkyl or R ¹ and R ² together with the one linking them

Carbon atom form a 5-, 6- or 7-membered cycloalkyl radical,

or a residue of the formula where R ³ and R ⁴ independently of one another are hydrogen or (C ₁ -C ₄ ) -alkyl,

means.

Preferred compounds of the formula (I) or their salts are

wherein

Z independently of one another halogen, in particular fluorine or chlorine, nitro, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or

Trifluoromethyl and

n is 0, 1 or 2,

as well as those compounds of formula (I) in which

X is hydroxy, (C ₁ -C ₄ ) alkoxy or a radical of the formula wherein R ^{3 is} hydrogen or CH ₃ and R ^{4 is} hydrogen or (C ₁ -C ₄ ) alkyl,

means. Compounds of the formula (I) in which Z, n and X are each preferred are particularly preferred

meanings mentioned. The present invention also relates to a process for the preparation of the compounds of the formula (I) and their salts, characterized in that a compound of the formula (II) (II)

wherein (Z) _{n has} the meanings given in formula (I), with a nitrile oxide of the formula (III) ( ^-) o - N = - COX (III)

wherein X has the meaning given in formula (I),

implements.

Non-polar organic solvents are suitable

Solvents, e.g. Ethers such as diethyl ether or THF.

The starting compounds of the formulas (II) and (III) are known from the literature (cf. J. Org. Chem. 25, 1160 (1960);

J. Med. Chem. 17: 549-552 (1974); J. Chem. Soc. Chem.

Commun. 1984, 968-969; and quotations mentioned there) or can be prepared analogously to known compounds.

The nitrile oxides of the formula (III) are generally prepared in situ from 2-halogeno-2-hydroximinoacetic acid (derivatives) under the action of bases and reacted directly with a compound of the formula (II) already contained in the reaction mixture. The reaction is preferably carried out at a temperature of from -15 ° C. to the boiling point of the

Solvent carried out especially at room temperature. The compounds of the formula (I) contain an asymmetry center on the C atom which is bonded to the oxygen atom in the isoxazoline ring. Corresponding enantiomeric forms can be carried out by customary methods, for example by racemate separation. A racemate separation is usually over diastereomeric salts of the compounds of formula I, in which X = OH, possible with optically active bases.

The compounds of the formula (I) reduce or prevent undesirable phytotoxic side effects which can occur when herbicides are used in crops of useful plants.

The compounds of the formula (I) and the herbicidal active compounds can be applied together or in succession in any order. The compounds of formula (I) are then able to reduce or completely eliminate harmful side effects of the herbicides in crop plants, without increasing the effectiveness of these herbicides against harmful plants

affect.

This makes the area of application more conventional

Plant protection products are expanded considerably.

Those compounds that have the property

Protecting crops against phytotoxic damage from herbicides is called "antidotes" or "safeners".

Herbicides whose phytotoxic side effects can be reduced by means of the compounds of formula (I) are e.g. Carbamates, thiocarbamates, haloacetanilides,

substituted phenoxy, naphthoxy,

Phenoxyphenoxy, benzyloxyphenoxy and

Heteroaryloxyphenoxy-carboxylic acid derivatives as well

Cyclohexanedione derivatives. Heteroaryloxy-phenoxycarboxylic acid derivatives are e.g. Quinolyloxy, quinoxalyloxy,

Pyridyloxy, benzoxazolyloxy, benzthiazolyloxy-phenoxy-carboxylic acid esters. Phenoxyphenoxy and are preferred

Heteroaryloxyphenoxycarboxylic acid esters. Lower alkyl, alkenyl and

Alkinylester in question.

For example, the following herbicides may be mentioned, without any restriction: A) herbicides of the phenoxyphenoxy-, benzylphenoxy- and heteroaryloxy-phenoxycarboxylic acid (C ₁ -C ₄ ) alkyl-,

- (C ₂ -C ₄ ) alkenyl and - (C ₃ -C ₄ ) alkynyl esters, such as

Methyl 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate, methyl 2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionate,

Methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate, methyl 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate, 2- (4- (2,4-dichlorobenzyl) phenoxy ) - methyl propionate,

Ethyl 4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-ene, ethyl 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionate, 2- (4- ( 3,5-dichloropyridyl-2-oxy) -phenoxy) -propionic acid propargyl ester,

Methyl 2- (4- (6-chlorobenzoxazol-2-yl-oxy) phenoxy) propionate, methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate,

Methyl 2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate, methyl 2- (4- (3-fluoro-5-chloropyridyl-2-oxy) phenoxy) propionate, 2- (4- ( 3-fluoro-5-chloropyridyl-2-oxy) phenoxy) propionic acid propargyl ester,

Methyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate, methyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate, 2- (4- (6-chloro-2- methyl quinolyloxy) phenoxy) propionate, 2- (4- (5-chloro-3-fluoropyridin-2-yloxy) phenoxy) thiopropionic acid 5-methoxycarbonylmethyl ester,

B) chloroacetanilide herbicides such as

N-methoxymethyl-2,6-diethylchloroacetanilide,

N- (3'-methoxyprop-2'-yl) methyl-6-ethylchloroacetanilide,

N- (3-methyl-1,2,4-oxdiazol-5-yl-methyl) -chloroacetic acid-2,6-dimethylanilide,

C) thiocarbamates such as

S-ethyl-N, N-dipropylthiocarbamate or S-ethyl-N, N-diisobutylthiocarbamate, D) Cyclohexanedione derivatives such as

Methyl 3- (1-allyloxyimino) butyl-4-hydroxy-6,6-dimethyl

2-oxocyclohex-3-encarboxylate

2- (N-ethoxybutyrimidoyl) -5- (2-ethylthiopropyl) -3-hydroxy-2-cyclohexen-1-one,

2- (N-ethoxybutyrimidoyl) -5- (2-phenylthiopropyl) -3-hydroxy-

2-cyclohexen-1-one,

2- (1-allyloxyiminobutyl) -4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol,

2- (1- (3-chloroallyloxy) iminobutyl) -5- (2-ethylthio) propyl) -

3-hydroxy-cyclohex-2-enone

2- (1- (ethoxyimino) butyl) -3-hydroxy-5- (thian-3-yl) cyclohex-2-enone or

2- (1-ethoxyiminopropyl) -5- (2,4,6-trimethylphenyl) -3-hydroxy-2-cyclohexen-1-one.

The quantitative ratio safener: herbicide can be within wide limits, preferably in the range between 1:10 and 10: 1, in particular between 2: 1 and 1:10. The optimal amounts of herbicide and safener depend on the type of herbicide or safener used and on the type of crop to be treated and can be determined from case to case by appropriate tests.

The main areas of application for the use of safeners are mainly cereal crops (wheat, rye, equipment, oats), rice, corn, sorghum, but also cotton, sugar beet, sugar cane and soybeans.

Depending on their properties, the safeners of the formula (I) can be used for pretreating the seed of the crop (dressing the seeds) or before sowing them into the

Furrows are introduced or together with the

Herbicide can be applied before or after emergence of the plants. Pre-emergence treatment includes both treatment of the area before sowing and the treatment of the sown but not overgrown areas. Co-application with the herbicide is preferred. Tank mixes or ready formulations can be used for this.

Depending on the indication and the herbicide used, the application rates of the compounds of the formula (I) can vary within wide limits and generally vary

between 0.01 and 10 kg of active ingredient per hectare.

The present invention therefore also relates to a process for the protection of crop plants from phytotoxic side effects of herbicides, which is characterized in that an effective amount of a compound of the formula (I) is applied to the plants or the cultivated area before, after or simultaneously with the herbicide is applied.

In addition, the compounds according to the invention have growth-regulating properties in crop plants. They regulate the plant's own

Metabolism and can thus facilitate harvesting such. B. by triggering desiccation, abscess and stunted growth. They are also suitable for general control and inhibition of

undesirable vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.

The compounds of the formula (I) or their combination with one or more of the herbicides mentioned or

Herbicide groups can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. As Formulation options are possible, for example:

Wettable powder (WP), emulsifiable concentrates (EC),

water-soluble powders (SP), water-soluble concentrates (SL), emulsions (EW), sprayable solutions, capsule suspensions (CS) dispersions based on oil or water, suspoemulsions,

Suspension concentrates (SC), dusts (DP), oil-miscible solutions (OL), pickling agents, granules (GR) in the form of

Micro, spray, elevator and adsorption granules,

Granules for soil or litter application, water-soluble granules (SG), water-dispersible granules (WG),

ULV formulations, microcapsules and waxes.

These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; van Valkenburg, "Pesticides Formulations",

Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray

Drying Handbook ", 3rd Ed. 1979, G. Goodwin Ltd. London. The necessary formulation aids such as

Inert materials, surfactants, solvents and others

Additives are also known and will be

described for example in: Watkins, "Handbook of

Insecticide Dust Diluents and Carriers ", 2nd Ed., Darland

Books, Caldwell N.J .; H.v. Olphen, "Intruduction to Clay

Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, N.Y.,

Marsden, Solvents Guide, 2nd Ed., Interscience, N.Y.

1950; McCutcheon's, "Detergents and Emulsifiers Annual",

MC Publ. Corp., Ridgewood N.J .; Sisley and Wood,

"Encyclopedia of Surface Active Agents", Chem. Publ. Co.

Inc., N.Y. 1964; Schönfeldt, "Interface Active

Ethylene oxide adducts ", Wiss. Verlagsgesellschaft., Stuttgart 1976;

Winnacker-Küchler, "Chemical Technology", Volume 7,

C. Hauser Verlag Munich, 4th edition 1986. On the basis of these formulations can also

Combinations with other pesticidal substances,

Manufacture fertilizers and / or growth regulators, e.g. in the form of a finished formulation or as a tank mix.

The invention therefore also relates to the compositions which comprise the compounds of the formula (I) according to the invention. Above all, these are, on the one hand, crop protection agents which contain one or more compounds of the formula (I) and the customary inert auxiliaries corresponding to the particular formulation type, and on the other hand herbicidal compositions which comprise a combination of compounds of the formula (I) and one or more herbicides and the particular

Formulation type contain appropriate common aids.

Spray powders are evenly dispersible in water

Preparations which, in addition to the active substance, contain a wetting agent, e.g. polyoxethylated

Alkylphenols, polyoxethylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates or

Alkylphenol sulfonates and dispersants, e.g.

sodium lignosulfonate,

2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,

dibutylnaphthalene-sulfonic acid sodium or also

Contain oleylmethyl tauric acid sodium.

Emulsifiable concentrates are made by dissolving the

Active ingredient in an organic solvent, e.g.

Butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons

Addition of one or more emulsifiers produced.

The following can be used as emulsifiers:

Alkylarylsulfonic acid calcium salts such as

Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide Condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or

Polyoxethylene sorbitol ester. Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays, such as kaolin, bentonite, pyrophillite, or diatomaceous earth.

Granules can either by spraying the active ingredient onto adsorbable, granulated inert material

be produced or by applying

Active ingredient concentrates using adhesives, e.g.

Polyvinyl alcohol, polyacrylic acid sodium or also

Mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be used in the production of

Fertilizer granules in the usual way - if desired in a mixture with fertilizers - are granulated. The agrochemical preparations generally contain 0.1 to 99 percent by weight, in particular 0.1 to 95 percent by weight,

Active ingredient of the formula (I), or active ingredient mixture antidote / herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid additive and 0 to 25

% By weight, in particular 0.1 to 25% by weight, of a surfactant.

The active substance concentration in wettable powders is e.g.

about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. With emulsifiable

Concentrates can have an active ingredient concentration of about 1 to 80% by weight, preferably 5 to 80% by weight. Dust-like formulations usually contain 1 to 25% by weight,

preferably 5 to 20 wt .-% of active ingredient, sprayable

Solutions about 0.2 to 25 wt .-%, preferably 2 to 20

% By weight of active ingredient. In the case of granules such as water-dispersible granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form. As a rule, the content of the water-dispersible granules is between 10 and 90% by weight. In addition, the active ingredient formulations mentioned contain

where appropriate, the usual adhesives, wetting agents, dispersing agents, emulsifying agents, penetrating agents, solvents, fillers or

Carriers.

To be used in the commercial form

present formulations, if necessary, in the usual

Way diluted e.g. with wettable powders, emulsifiable

Concentrates, dispersions and water dispersible

Granules using water. Dust-like preparations,

Soil or scatter granules as well as sprayable solutions are usually no longer used before use

other inert substances diluted. With the external conditions such as temperature, humidity, the type of herbicide used, etc. varies the

required application rate of the compounds of formula (I). It can fluctuate within wide limits, e.g. between 0.005 and 10.0 kg / ha or more of active substance, but is preferably between 0.01 and 5 kg / ha.

The following examples serve to illustrate the invention: A. Formulation examples a) A dusting agent is obtained by adding 10 parts by weight

a compound of formula (I) and 90 parts by weight of talc or inert and mixed in a hammer mill

crushed. b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of a compound of the formula (I), 64 parts by weight of quartz containing kaolin as an inert substance, and 10 parts by weight of lignosulfonic acid

Potassium and 1 part by weight of oleoylmethyl tauric acid sodium as a wetting and dispersing agent and mixed in one

Pin mill grinds. c) A water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of formula (I) with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. -Share paraffinic mineral oil

(Boiling range e.g. approx. 255 to above 277 ° C) mixed and ground in a friction ball mill to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight

ethoxylated nonylphenol as an emulsifier. e) A water-dispersible granulate is obtained

by one

75 parts by weight of a compound of the formula I,

10 "calcium lignosulfonic acid,

5 "sodium lauryl sulfate,

3 "polyvinyl alcohol and

7 "kaolin mixes, grind on a pin mill and powder in a fluidized bed by spraying water as

Granulating liquid granulated. f) A water-dispersible granulate is also obtained by 25 parts by weight of a compound of the formula (I),

5 "2,2'-dinaphthylmethane-6,6 ^, disulfonic acid

Sodium,

2 "oleoylmethyl tauric acid sodium,

1 part by weight of polyvinyl alcohol,

17 parts by weight of calcium carbonate and

50 "water homogenized and pre-shredded on a colloid mill, then ground on a pearl mill and the like

The suspension obtained is atomized and dried in a spray tower using a single-component nozzle.

B) Chemical examples

5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (Example No. 93)

18.8 ml of triethylamine are added dropwise to 10.7 g of 2,4-dichloro-1-allylbenzene in 270 ml of ether. A solution of 20.55 g of 2-chloro-2-hydroximino-acetic acid ethyl ester in 270 ml of ether is then slowly added dropwise within 5 hours.

The mixture is then stirred for 24 hours, extracted with water, the ether phase dried and ether distilled off. This gives 35.5 g (98% of theory) of the product described above with a refractive index of = 1.534.

2-chloro-2-hydroximino-acetic acid ethyl ester

(Starting material for example No. 93)

69.8 g of glycine ethyl ester hydrochloride are placed in 120 ml of water and 41 ml of concentrated hydrochloric acid. At -10 ° C., 38 g of NaNO ₂ in 60 ml of water are then added dropwise within 1 hour. After half an hour, a further 42.5 ml of concentrated hydrochloric acid are added and then a further 38 g of NaNO ₂ in 60 ml of water within 1 hour. The mixture is stirred at -10 ° C for 1 hour. It is then extracted with ether and washed the ether phase several times with water. The ether is distilled off and the crystals are dried. 38 g (50% of theory) of 2-chloro-2-hydroximinoacetic acid ethyl ester with a melting point of 81-82 ° C. are obtained.

In the following Table I the above-mentioned example is listed together with further examples which can be produced in an analogous manner.

The analog isoxazoline carboxylic acids can be obtained from the

corresponding esters or the isoxazoline esters optionally from the corresponding carboxylic acids in principle

known methods are produced.

H

* -θ O

O

Ω

>! U)

C. Biological examples

example 1

Wheat and barley were grown in the greenhouse in plastic pots up to the 3-4th stage and then with

Invention compounds and herbicides in the

Treated post-emergence. The herbicides and the

Compounds of the formula (I) were applied in the form of aqueous suspensions or emulsions with a water application rate of the equivalent of 800 l / ha. 3-4 weeks after treatment, the plants were visually examined for each type of

Damage caused by the applied herbicides was rated, taking into account in particular the extent of the continued growth inhibition. The evaluation was made in percentages compared to untreated controls.

The results from Table II illustrate that the compounds according to the invention show severe herbicide damage

Can effectively reduce crops.

Even if the herbicides are overdosed, severe damage to crops is significantly reduced and less damage is completely eliminated. Mixtures of herbicides and compounds according to the invention are therefore outstandingly suitable for selective weed control in cereal crops.

Abbreviations:

TRAE = Triticum aestivum (wheat)

HOVU = Hordeum vulgare (barley)

a.i. = Active substance (i.e. based on pure active substance)

H = 2- (4- (6-chlorobenzoxazol-2-yloxy) phenoxypropionic acid ethyl ester (fenoxaprop-ethyl)

Safener No. = s. No. of the preparation example from Table I

Claims

PATENT CLAIMS

1. Compounds of formula (I) or their salts

(I),

wherein

Z independently of one another halogen, nitro, cyano or

are substituted, or furthermore amino, mono- or

Dialkylamino, phenyl or phenoxy, where phenyl and phenoxy are independently unsubstituted or substituted one or more times by halogen or haloalkyl, or two adjacent substituents Z together for a divalent group of the formula -OCH ₂ O-, -S-CH ₂ -O - or -S-CH ₂ -S-, which is unsubstituted or substituted by alkyl, n is an integer from 0 to 5,

X is hydroxy or alkoxy, alkenyloxy, alkynyloxy, alkylthio or cycloalkoxy, the five latter radicals being unsubstituted or mono- or polysubstituted by radicals from the group alkoxy, alkylthio-, mono- and dialkylamino, phenyl, substituted phenyl, cyano and halogen

are substituted, or

also phenoxy or substituted phenoxy,

also trialkylsilylmethoxy, a radical of the formula

wherein each R is hydrogen or alkyl, Z ^1, independently of Z, has the meanings given above for Z and n ^{1 is} an integer from 0 to 5, or

furthermore amino, mono- or dialkylamino, cycloalkylamino, hydrazino, alkyl- or dialkylhydrazino, pyridino,

Morpholino, dimethylmorpholino, a radical of formula X

mean.

2. Compounds or their salts according to claim 1, characterized in that in formula (I)

Z independently of one another halogen, nitro, cyano, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio, where the alkyl, alkoxy and alkylthio groups are unsubstituted or mono- or are substituted several times by halogen atoms, in particular fluorine or chlorine, (C ₃ -C ₆ ) cycloalkyl which is unsubstituted or substituted by (C ₁ -C ₄ ) alkyl, amino, (C ₁ -C ₄ ) alkylamino, di- ( C ₁ -C ₄ ) alkylamino,

Hydroxymethyl, (C ₁ -C ₄ ) alkoxy-methyl, phenyl or phenoxy, where phenyl and phenoxy are unsubstituted or one or more times by halogen or simply by trifluoromethyl or by one or more halogen atoms and one Trifluoromethyl is substituted, or two adjacent substituents Z represent the divalent group -O-CH ₂ -O-, -S-CH ₂ -O- or -S-CH ₂ -S- and

n 0, 1, 2 or 3

mean.

3. Compounds or their salts according to claim 1 or 2, characterized in that

X hydroxy, -OCH ₂ Si (CH ₃ ) ₃ , (C ₃ -C ₆ ) cycloalkoxy,

Phenyl (C ₁ -C ₆ ) alkoxy, phenoxy, (C ₂ -C ₆ ) alkenyloxy,

(C ₂ -C ₆ ) alkynyloxy, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkylthio, the alkoxy or alkylthio group being unsubstituted or mono- or disubstituted by (C ₁ - C ₂ ) alkoxy, mono- or di- (C ₁ -C ₆ ) alkylamino, (C ₁ -C ₂ ) alkylthio, cyano or substituted one or more times by halogen,

a rest of the formula

wherein

R ¹ and R ² independently of one another are (C ₁ -C ₄ ) alkyl or R ¹ and R ² together with the one linking them Carbon atom form a 5-, 6- or 7-membered cycloalkyl radical,

or a residue of the formula

where R ³ and R ⁴ independently of one another are hydrogen or (C ₁ -C ₄ ) -alkyl,

means.

4. Compounds or their salts according to one or more of claims 1 to 3, characterized in that

Trifluoromethyl and

n 0, 1 or 2 and

X is hydroxy, (C ₁ -C ₄ ) alkoxy or a radical of the formula ^ό wherein R ^{3 is} hydrogen or CH ₃ and R ^{4 is} hydrogen or (C ₁ -C ₄ ) alkyl,

mean.

5. A process for the preparation of the compounds of formula (I) or their salts defined according to one or more of claims 1 to 4, characterized in that one

Compound of formula (II)

(II) wherein (Z) _{n has} the meanings given in formula (I), with a nitrile oxide of the formula (III) (III)

wherein X has the meaning given in formula (I),

implements.

6. Plant protection agents, characterized in that they contain compounds of formula (I) or their salts according to one or more of claims 1 to 4 and inert additives.

7. Selective herbicidal compositions, characterized in that they contain herbicides in combination with compounds of the formula (I) or their salts which are defined according to one or more of claims 1 to 4.

8. Composition according to claim 7, characterized in that they are herbicidal active ingredients from the group carbamates,

Thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy, phenoxyphenoxy, benzyloxyphenoxy and

Heteroaryloxyphenoxy carboxylic acid derivatives and

Cyclohexanedione derivatives included.

9. A method for controlling unwanted plants in crops, characterized in that

Herbicide in combination with compounds of formula (I) or their salts as defined in one or more of claims 1 to 4, or applied to the plants, plant seeds or the cultivated area.

10. Process for protecting crops against

phytotoxic side effects of herbicides, thereby

characterized in that herbicides in combination with one or more of claims 1 to 4 defined compounds of formula (I) or their salts on the

Plants, plant seeds or the acreage applied.

11. Use of compounds of formula (I) or their salts as defined in one or more of claims 1 to 4 for protecting phytotoxic side effects of herbicides.