WO1993016062A1

WO1993016062A1 - Mixtures of optically active cyclohexenone oxime ethers, process and intermediate products for their production and their use as herbicides

Info

Publication number: WO1993016062A1
Application number: PCT/EP1993/000212
Authority: WO
Inventors: Ulf Misslitz; Norbert Meyer; Juergen Kast; Harald Rang; Hardo Siegel; Helmut Walter; Karl-Otto Westphalen; Matthias Gerber; Uwe Kardorff
Original assignee: Basf Aktiengesellschaft
Priority date: 1992-02-13
Filing date: 1993-01-30
Publication date: 1993-08-19
Also published as: EP0625974A1; JPH07505866A; RU94044433A; ZA93970B; DE4204206A1; HU216276B; KR950700271A; HU9402353D0; CA2129121A1; BR9305882A; HUT68901A; TW232646B

Abstract

Mixtures of optically active cyclohexenone oxime ethers, with an R and S configuration in the oxime ether section of formula (I) where R1 = C1-C6 alkyl; X = NO2, CN, halogen, C1-C4 alkyl, C1-C4 halogen alkyl; n = 0-3 or 1-5 if all X substituents are halogen; R2 = C1-C4-alkoxy-C1-C6-alkyl, C1-C4-alkythio-C1-C6-alkyl, optionally substituted C3-C7 cycloalkyl, optionally substituted C5-C7 cycloalkenyl, optionally substituted 5-membered saturated heterocyclic ring containing 1 or 2 oxygen and/or sulphur atoms, optionally substituted 6 or 7-membered heterocyclic ring with 1 or 2 non-adjacent oxygen and/or sulphur atoms which may be saturated or singly or doubly unsaturated, optionally substituted aromatic 5-membered heterocyclic ring containing one to two N atoms and one O or S atom, phenyl or pyridyl both of which may bear 1-3 substituents: halogen, NO2, CN, alkyl, alkoxy, alkylthio, halogen alkyl, alkenyloxy, alkinyloxy and/or -NRaRb; Ra = H, alkyl, alkenyl or alkinyl and Rb = H, alkyl, alkenyl, alkinyl, acyl or optionally substituted benzoyl; and their agriculturally usable salts, and esters of C¿1?-C10 carboxylic acids and inorganic acids of compounds (I), with the proviso that the mixtures contain at least 75 mol % isomers with R configuration in the oxime ether part.

Description

Mixtures of optically active cyclohexenone oxime ethers, processes and intermediates for their preparation and their use as herbicides

description

The present invention relates to new mixtures of optically active cyclohexenone oxime ethers with R and S configuration in the oxime ether part of the general formula I.

in which the substituents have the following meaning:

R ^{1 is} a Ci-Cβ alkyl group;

X nitro, cyano, halogen, -C -C alkyl, -C -C ₄ haloalkyl; n is 0 to 3 or 1 to 5 if all X is halogen; 2 a Cχ-C ₄ alkoxy-Cι-C ₆ - ^* _-H *} ^* ----- _^ - ^* -4 ^ _^ kylgruppe;

a C ₃ -C -cycloalkyl group or a C ₅ -C -cycloalkenyl group, where these groups can, if desired, carry one to three substituents, selected from a group consisting of C 1 -C ₄ alkyl, C 1 -C ₄ alkox , Ci-C ^ alkylthio, -C-C ₄ haloalkyl, hydroxyl and halogen;

a 5-membered saturated heterocycle which contains one or two oxygen and / or sulfur atoms as heteroatoms and which, if desired, can also carry one to three substituents, selected from a group consisting of C 1 -C ₄ -alkyl, Cι- C ₄ -alkoxy, C ₄ alkylthio and _{Cι-C4-haloalkyl;} a 6- or 7-membered saturated or mono- or di-unsaturated heterocycle which contains one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as heteroatoms,

if desired, the heterocycle can also carry one to three substituents selected from a group consisting of hydroxyl, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cι-C ₄ ~ alkylthio and Cχ-C ₄ - Haloalkyl;

a 5-membered heteroaromatic containing one to three heteroatoms selected from a group consisting of one or two nitrogen atoms and one oxygen or sulfur atom,

where the heteroaromatic if desired, can carry one to three substituents selected from a group be¬ standing from halogen, cyano, C alkyl, C] _-C4 ~ alkoxy, Cι-C ₄ alkylthio, Cι-C ₄ - Haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy and Cχ-C ₄ alkoxy-Cχ-C ₄ alkyl;

a phenyl or pyridyl group, these aromatics optionally being able to carry one to three substituents selected from a group consisting of halogen, nitro, cyano, C 1 -C ₄ -alkyl, C ₄ -C ₄ -alkoxy, C 1 -C 3 -alkylthio,

Cχ-C haloalkyl, C ₃ -C s-alkenyloxy, C ₃ ~ C ₆ -alkynyloxy and an amino group -NR ^a Pk, in which -

R ^{a is} hydrogen, Cχ-C ₄ alkyl, C ₃ -C ₆ alkenyl or C3-Ce alkynyl and

R ^{b is} hydrogen, -CC ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, Cχ-Cg-acyl or benzoyl, which, if desired, can in turn carry one to three residues, selected from a group consisting of nitro, cyano, halogen, C 1 -C ₄ alkyl, C 1 -C ₄ alkoxy, C 1 -C ₄ alkylthio and Cχ-C ₄ haloalkyl;

and the agriculturally useful salts and esters of Cχ-Cχo-carboxylic acids and inorganic acids of the compounds I, with the proviso that the mixtures contain at least 75 mol% of isomers with R configuration in the oxime ether part.

In addition, the invention relates to a process for the preparation of these compounds, their use as herbicides and herbicidal compositions which contain these compounds as active substances.

The invention further relates to new mixtures of optically active hydroxylamines with R and S configuration of the formula III

in which

X for nitro, cyano, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ halogen alkyl "and n for 0 to 3 or 1 to 5 in the event that all X are halogen,

stand, with the measure that the mixtures contain at least 75 mol% of isomers with R configuration, and a process for the preparation of the intermediates III.

Herbicidal cyclohexanediones of the formula I 'are already from the literature

known, where R ^c , R ^d and R ^e stand inter alia for the following meanings:

US 4,440,566 (R ^c = ethyl, propyl; R ^d = benzyi; R = 2-ethylthiopropyl);

EP-A 238 021 and EP-A 125 094 (R ^c = ethyl, propyl;

R ^d = benzyi, but-2-enyl; R ^e = more substituted

5-membered heteroaryl radical);

EP-A 80 301 (R ^c = ethyl, propyl; R ^d = benzyi, but-2-enyl; R ^e = substituted phenyi);

DE-A 38 38 309 (R ^c = ethyl, propyl; R ^d = substituted

4-phenylbutylene or 4-phenylbutenylene;

R ^e = substituted 5- to 7-membered heterocycle);

EP-A 456 112 (R <= ethyl, propyl; R ^d = substituted 3-phenoxypropylene or 2-phenoxyethylene;

R ^e = substituted 5- to 7-membered heterocycle).

However, the herbicidal properties of these compounds, in particular with regard to their selectivity against grass weeds in grassy crop plants, can only give satisfactory results.

The invention was therefore based on new mixtures of cyclohexenone oxime ethers with improved selectivity against grass weeds in grassy crops such as rice and maize.

We have found that this object is achieved by the mixtures of optically active cyclohexenone oxime ethers I defined at the outset. Herbicidal compositions containing these mixtures have also been found.

The mixtures of optically active cyclohexenone oxime ethers I can be obtained in various ways, preferably in a manner known per se from already known cyclohexenones of the formula II (DE-A 38 38 309, EP-A 243 313,

EP-A 456 112) and the corresponding mixtures of optically active hydroxylamines of the formula III (cf. EP-A 169 521):

II III

A suitable salt of the hydroxylamines III, in particular their hydrochloride, is preferably used and the reaction is carried out in the heterogeneous phase in an inert solvent, for example in dimethyl sulfoxide, in an alcohol such as methanol, ethanol and isopropanol, in an aromatic hydrocarbon such as benzene and Toluene, in a chlorinated hydrocarbon such as chloroform and 1,2-dichloroethane, in an aliphatic hydrocarbon such as hexane and cyclohexane, in an ester such as ethyl acetate or in an ether such as diethyl ether, dioxane and tetrahydrofuran.

The reaction is carried out in the presence of a base, a base amount of about 0.5 to 2 mol equivalents, based on the ammonium compound, normally being sufficient.

Suitable bases are, for example, carbonates, bicarbonates, acetates, alcoholates or oxides of alkali or alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide. Organic bases such as pyridine and tert. Amines such as triethylamine are suitable. The reaction is preferably carried out in methanol using sodium hydrogen carbonate as the base. A variant of the method consists in the reaction without base with the free hydroxylamine bases III, z. B. in the form of an aqueous solution; depending on the solvent used for the compound II, a one- or two-phase reaction mixture is obtained.

Suitable solvents for this variant are, for example, alcohols such as methanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatic, optionally chlorinated hydrocarbons such as hexane, cyclohexane,

Methylene chloride, toluene and 1,2-dichloroethane, esters such as ethyl acetate, nitriles such as acetonitrile and cyclic ethers such as dioxane and tetrahydrofuran.

The cyclohexenone II and the mixture of optically active hydroxylamines III or their salts are expediently used in an approximately stoichiometric ratio, but in some cases an excess of one or the other component, up to about 10 mol%, can also be advantageous .

The reaction temperature is generally between 0 ° C and the boiling point of the reaction mixture, preferably between 20 and 80 ° C.

The reaction is complete after a few hours. The product can be prepared in the usual way, e.g. B. by concentrating the mixture, distributing the residue in methylene chloride / water and distilling off the solvent under reduced pressure.

Special conditions regarding the pressure are not to be considered; in general, therefore, one works at normal pressure or under the autogenous pressure of the respective diluent.

Because of their acidic character, the optically active cyclohexenone oxime ether I can form salts of alkali or alkaline earth metal compounds and enol esters. Alkali metal salts of the compounds I can be obtained by treating the 3-hydroxycyclohexenone compounds with sodium or potassium hydroxide or alcoholate in aqueous solution or in an organic solvent such as methanol, ethanol, acetone and toluene.

Other metal salts such as manganese, copper, zinc, iron, calcium, magnesium and barium salts can be prepared from the sodium salts in a conventional manner, as can ammonium and phosphonium salts using ammonia,

Phosphonium, sulfoniu or sulfoxonium hydroxides.

The esters of the compounds I are also available in the usual way (see e.g. Organikum, VEB Deutscher erlag der Wissenschaften, 17th edition, Berlin 1988, pp. 405-408).

The new mixtures of optically active hydroxylamines III can be prepared from known precursors in a number of known process steps:

VII L = a leaving group, e.g. B. halogen such as chlorine, bromine and

The optically active alkylating agent V {Tetrahedron Lett is preferably coupled. 22., 5493 (1988); J. Org. Chem. 51, 3587 (1987); EP-A 172 719; EP-A 230 379; No. 4,841,079}, but if desired also the optically active carbinol IV {Chem. Pharm. Bull. 3_3_, 1955 (1985)} according to the Mitsunobu variant {Synthesis 1, 1981; J. Med. Chem. H, 187 (1990)}, with a cyclic hydroxyimide VI and cleaves the resulting protected hydroxylamine derivative VII to free optically active hydroxylamine III, e.g. B. with 2-aminoethanol.

In the cyclic hydroxyimides VI, D is z. B. for C ₂ -C ₃ alkylene, C ₂ ~ alkenylene or a 5- or 6-membered ring with optionally a nitrogen fatom, which can be saturated, partially unsaturated or aromatic, for. B. for phenylene, pyridinylene, cyclopentylene, cyclohexylene or cyclohexenylene.

For example, the following substances can be used:

The reaction of the optically active alkylating agent V with the hydroxyimides VI is advantageously carried out in the presence of a base. In principle, all bases which are capable of deprotonating the hydroxyimides VI without attacking the imide system are suitable. These are especially the so-called non-nucleophilic bases.

Examples include mineral bases such as alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal hydrogen carbonates, organic bases such as aliphatic, cycloaliphatic and aromatic tertiary amines. Mixtures of these bases can also be used.

The following are examples of individual compounds: sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, the hydrogen carbonates of these metals, trimethylamine, triethylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylaniline, 4- (N, N- Dimethylamino) pyridine, diazabicyclooctane, diazabicycloundecane, N-methylpiperidine, 1,4-dimethylpiperazine,

Pyridine, quinoline, bipyridine, phenanthroline. The inexpensive bases sodium and potassium carbonate are preferred.

The base is generally added in equivalent amounts up to an excess of 5 equivalents, based on the hydroxyimide. A higher excess is possible, but usually does not bring any additional advantages. It is also possible to use a small amount of base. However, a base amount of 1 to 3, in particular 1 to 2 equivalents, based on the hydroxyimide VI, is preferably used.

The use of nucleophilic bases, e.g. B. alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, is also possible. In this case it is advantageous to use the base in equivalent amounts with respect to the hydroxyimide VI in order to prevent nucleophilic attack of the hydroxyl ions on the carbonyl function of the imide grouping.

The optically active alkylating agent V is expediently reacted with the hydroxyimides VI in a solvent which is reacted under the reaction conditions behaves inertly. Advantageous solvents are e.g. B. polar, aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and cyclic ureas. The amount of solvent is generally not critical.

The reaction of the optically active alkylating agents V with the hydroxyimides VI can also be carried out using phase transfer catalysis. In this case, two-phase solvents, preferably chlorinated hydrocarbons, are used with water.

Suitable phase transfer catalysts are the quaternary ammonium and phosphonium salts, polyethylene glycols, polyethylene glycol ethers and crown ethers, as are used, for example, for such purposes. B. in Dehmlow et al., Phase Transfer Catalysis, pp. 37-45 and pp. 86-93, Verlag Chemie, Weinheim 1980.

The phase transfer catalysts are expediently used in amounts of 1 to 10% by volume, preferably in amounts of 3 to 5% by volume, based on the volume of the reaction mixture.

The reaction of the optically active alkylating agents V with the hydroxyimides VI generally takes place in the temperature range between 0 and 140 ° C., preferably between 2 and 100 ° C., in particular between 40 and 80 ° C. The procedure is advantageously such that the hydroxyimide VI is initially introduced together with the base in the solvent and the alkylating agent V is metered into this solution. It may prove to be advantageous if the hydroxyimide is added at a lower temperature, for example at 0 to 50 ° C., and the reaction mixture is heated to the actual reaction temperature only after this addition.

When the reaction has ended, water is expediently added to the cooled reaction mixture, the hydroxylamine derivatives VII formed separating out as crystalline solids or as oils. The hydroxylamine derivatives obtained in this way can, if desired, by Recrystallization or further purified by extraction.

The hydroxylamine derivatives VII can be temporarily stored or immediately converted into the optically active hydroxylamines III with a free amino group.

This conversion can be carried out according to methods known per se, as described, for example, in DE-A 36 15 973 and the documents cited therein. The method according to DE-A 36 15 973 is preferably used after the optically active hydroxylamines III have been released by means of ethanolamine. It is also possible to release the optically active hydroxylamines III with the aid of other bases such as aqueous mineral bases, with amines, hydrazines, hydroxylamines or with aqueous acids.

The optically active hydroxylamines III can be isolated from the reaction mixtures obtained by these processes by means of customary workup methods, for example by extraction or by crystallization. To increase the tendency of these hydroxylamines III to crystallize, it can often be beneficial to convert them into their salts with mineral acid or organic acids. For this purpose, dilute solutions of these acids are generally mixed with

Hydroxylamine derivatives implemented, expediently in equivalent amounts. The hydroxylammonium salts obtained can, like the optically active hydroxylamines III (with free amino group), be further processed directly to give the optically active cyclohexenone oxime ethers of the formula I or, if desired, can also be stored.

The optical purity of the intermediates III and the cyclohexenone oxime ether I depends on the optical purity of the carbinols IV or alkylating agent V used. According to the invention, R-configured carbinols IV or R-configured alkylating agents V are used, with the highest possible optical purity, so that in the preparation of the optically active hydroxylamines III and the optically active cyclohexenone oxime ethers I, isomer mixtures are obtained whose Proportion of isomers with R con figuration on the methyl-substituted C atom (in the oxime ether part) is at least 75 mol%, in particular 90 to 100 mol%.

The optically active cyclohexenone oxime ethers I can be obtained in the preparation as isomer mixtures, both E / Z isomer mixtures (position of the oxime ether part relative to R ¹ ) and diastereoisomer mixtures being possible. If desired, the isomer mixtures can be prepared by the customary methods, for. B. by chromatography or by crystallization.

The optically active cyclohexenone oxime ethers I can be written in several tautomeric forms, all of which are encompassed by the invention.

The collective terms used in the definition of the substituents

- halogen,

Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio,

Cχ-C ₄ haloalkyl,

C ₂ -C ₆ alkenyl, C ₂ -Cg alkenyloxy,

C ₃ -Cg alkenyl, C ₃ -C _δ alkenyloxy, C ₃ -Cg alkynyl, C ₃ -C ₅ alkynyloxy,

C -Ce acyl

are short notations for an individual enumeration of the individual group members. All alkyl, alkoxy, alkylthio, haloalkyl, alkenyl, alkenyloxy, alkynyl and alkynyloxy parts can be straight-chain or branched. The haloalkyl parts can carry identical or different halogen atoms.

Specifically mean, for example

Halogen: fluorine, chlorine, bromine and iodine;

Cχ-C-alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl; Cχ-C4-alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy;

- Cχ-C ₄ alkylthio: methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio;

Cχ-C ₄ haloalkyl: fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-di-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2 , 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

C ₂ -C ₆ alkenyl: ethenyl and C ₃ -C ₆ alkenyl such as 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1- propenyl, l-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pen _, tenyl, 3-pentenyl, 4-pentenyl, 1-methyl -l-butenyl, 2-methyl-1-butenyl, 3-methyl-l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl -3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl, 1,2-di - methyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl -l-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1,2-dimethyl-l-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl 1-butenyl, l, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-l-butenyl, 1-ethyl-l-butenyl, l-ethyl-2-butenyl, l- Ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl- l-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

C ₂ -Ce alkenyloxy: ethenyloxy and Cs-Cs alkenyloxy such as 2-propenyloxy, 2-butenyloxy, 3-butenyloxy, l-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-pentenyloxy, 3 -Pentenyloxy, 4-pentenyloxy, l-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, l-methyl-3-butenyloxy, 2 ~ methyl-3-butenyloxy, 3 -Methyl-3-butenyloxy, 1, l-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy, l-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy , 5-hexenyloxy, 1-methyl-2-pentenylox, 2-methyl-2-pentenyloxy, 3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy , 2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy, 1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl -4-pentenyloxy, 4-methyl-4-pentenyloxy, 1,1-dimethyl-2-butenyloxy, 1,2-dimethyl-2-butenyloxy, 1,2-dimethyl-3-butenyloxy, 1,3 -Dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy, 2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy , l-ethyl-2-butenyloxy, l-ethyl-3-butenyloxy, 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, l-ethyl- l-methyl-2-propenyloxy and l-ethyl-2-methyl-2-propenyloxy;

In view of their herbicidal activity, cyclohexenones of the formula I are preferred, in which the variables have the following meaning:

R ¹ Cχ-C ₆ alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, preferably ethyl and propyl;

X nitro, cyano,

- Halogen, preferably fluorine, chlorine and bromine;

- Cχ-C alkyl, preferably methyl;

- Cχ-C ₄ haloalkyl, preferably difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl and pentafluoroethyl; halogen is particularly preferred; n is 0 to 3 or 1 to 5 if all X is halogen; 0 to 3 is particularly preferred;

R2 - a Cχ-C ₆ alkyl group such as methyl, ethyl, n-propyl,

1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethybutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl and l- Ethyl-2-methylpropyl, where the alkyl group is substituted by Cχ-C ₄ -alkoxy, preferably methoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy, or by Cχ-C ₄ -alkylthio, preferably methylthio and ethylthio, and preferably in the 1-, 2- or 3-position; 2-ethylthiopropyl is very particularly preferred;

a C ₃ -C cycloalkyl group or a C ₅ -C cycloalkenyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl and

Cycloheptenyl, where these groups can be unsubstituted or can carry one to three of the following substituents:

Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio and Cχ-C ₄ haloalkyl; is very particularly preferred

1-methylthio-1-cyclopropyl;

a 5-membered saturated heterocycle such as tetrahydrofuranyl, tetrahydrothienyl, dioxolanyl, dithiolanyl and oxathiolanyl, in particular tetrahydrofuranyl, tetrahydrothienyl and dioxolanyl, where these rings can be unsubstituted or can carry one to three substituents selected from one group selected from a group selected from Cχ -C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio and Cχ-C ₄ haloalkyl; a 5-membered heteroaromatic such as pyrrolyl, pyrazolyi, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, furanyl and thienyl, in particular isoxazolyl and furanyl, where the 5-membered heteroaromatic may be unsubstituted or carry one to three selected substituents from a group consisting of Cχ-C ₄ alkyl, Cι-C ₄ alkoxy, Cχ-C ₄ alkylthio, C — C ^ haloalkyl and Cχ-C ₄ alkoxy-Cι-C ₄ alkyl such as methoxymethyl , 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-methoxy-1-methylethyl, ethoxymethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 2-ethoxy-l-methylethyl and 1-ethoxy -l-methylethyl, preferably methoxyethyl and ethoxyethyl,

C ₂ -C ₆ alkenyl such as enthenyl and C ₃ -C ₅ alkenyl, preferably 1-methylethen-l-yl,

C ₂ ~ C ₆ alkenyloxy such as ethenyloxy and C ₃ -C ₅ alkenyloxy, especially 1-methylethen-l-yloxy,

a 6- or 7-membered heterocycle of

a) can be saturated, for example tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl and dioxepan-5-yl, b) can be mono- or di-unsaturated, for example dihydropyran 3-yl, dihydropyran-4-yl, dihydrothiopyran-3-yl and dihydrothiopyran-4-yl, it being possible for the heterocycles to be unsubstituted or to carry one to three substituents selected from a group consisting of hydroxyl, halogen, C-. -C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio and Cχ-C ₄ haloalkyl; tetrahydropyran-3-yl, tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl are very particularly preferred;

a phenyi or pyridyl group, both of which can be unsubstituted or can carry one to three substituents, selected from a group consisting of Cχ-C ₄ alkyl, Cι-C ₄ alkoxy, Cχ-C ₄ alkylthio, Cχ-C ₄ haloalkyl, C ₃ -C ₆ alkenyloxy, preferably

2-propenyloxy and 2-butenyloxy, C ₃ -Cg-alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, l-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-methyl-2-butynyloxy, 1, 1-dimethyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, l-methyl-2-pentynyloxy, l-methyl-3-pentynyloxy, l-methyl-4-pentynyloxy, 2-methyl-3-pentynyloxy, 2-methyl-4-pentynyloxy, 3-methyl-4-pentynyloxy, 4-methyl-2-pentynyloxy, 1, l-dimethyl-2-butynyloxy, 1, l-dimethyl-3-butynyloxy, l, 2-dimethyl 3-butynyloxy, 2,2-dimethyl-3-butynyloxy, l-ethyl-2-butynyloxy, l-ethyl-3-butynyloxy,

2-ethyl-3-butynyloxy and l-ethyl-l-methyl-2-propynyloxy, preferably 2-propynyloxy and 2-butynyloxy; one of the three substituents on the phenyl or pyridyl ring can also be an amino group -NR ^a R ^b , where

R ^a for

Hydrogen,

Cχ-C ₄ alkyl, preferably methyl and ethyl,

C ₃ -C ₆ alkenyl, preferably 2-propenyl and 2-butenyl, C ₃ -C ₆ alkynyl, preferably 2-propynyl and 2-butynyl, and

R ^{b represents} hydrogen, Cχ-C ₄ alkyl, preferably methyl and ethyl,

C ₃ -C ₆ alkenyl, preferably 2-propenyl and 2-butenyl, C ₃ -C ₆ alkynyl, preferably 2-propynyl and 2-butynyl, or for Cχ-C ₆ ~ acyl such as acetyl, propionyl, butyryl, 2nd -Methyl-propionyl, n-pentanoyl, 2-methylbutyryl, 3-methylbutyryl, 2,2-dimethylpropionyl, n-hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2,2-dimethylbutyryl, 2 , 3-dimethylbutyryl, 3, 3-dimethylbutyryl and 2-et ylbutyryl, preferably acetyl and propionyl,

or benzoyl, which may be unsubstituted or in turn carry one to three radicals, selected from a group consisting of nitro, cyano, halogen, preferably fluorine, chlorine and bromine, Cχ-C ₄ alkyl, preferably methyl, Cχ-C ₄ alkoxy , preferably methoxy and ethoxy, Cχ-C ₄ alkylthio, preferably methylthio, and Cχ-C ₄ haloalkyl, preferably trifluoromethyl, ^•

stand.

Suitable salts of the compounds of the formula I are agriculturally useful salts, for example alkali metal salts, in particular the sodium or potassium salt, alkaline earth metal salts in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and ammonium salt , Phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.

Esters of Cχ-Cχo-carboxylic acids include, in particular, Cχ-C ₆ -alkyl carboxylic acids such as methyl carboxylic acid (acetic acid), ethyl carboxylic acid (propionic acid), propyl carboxylic acid (butyric acid), 1-methylethyl carboxylic acid (isobutyric acid), butyl carbyl carbonate, 1-methyl propyl carbonate - Acid, 2-methylpropylcarboxylic acid, 1, 1-dimethylethylcarboxylic acid, pentylcarboxylic acid, 1-methylbutylcarboxylic acid, 2-methylbutylcarboxylic acid, 3-methylbutylcarbonic acid, 1, 1-dimethylpropylcarboxylic acid, 1,2-dimethylpropylcarboxylic acid, 2.2 -Dimethylpropylcarboxylic acid, 1-ethylpropylcarboxylic acid, benzoic acid as well as halogen substituted benzoic acids, hexylcarboxylic acid, 1-methylpentylcarboxylic acid, 2-methylpentylcarboxylic acid, 3-methylpentylcarboxylic acid, 4-methylpentylcarboxylic acid, 1, 1-dimethylbutylcarboxylic acid, 1, 1-dimethylbutylcarboxylic acid, Dimethylbutylcarboxylic acid, 2,2-dimethylbutylcarboxylic acid, 2, 3-dimethylbutylcarboxylic acid, 3, 3-dimethylbutylcarboxylic acid, 1-ethylbutylcarboxylic acid, 2-ethylbutylcarboxylic acid right, 1, 1,2-trimethylpropylcarboxylic acid,

To understand 1,2,2-trimethylpropylcarboxylic acid, 1-ethyl-l-methylpropylcarboxylic acid and l-ethyl-2-methylpropylcarboxylic acid. Manufacturing examples

(R) -2- [1- [2- (4-chlorophenoxy) propyloxyimino] propyl] -3-hydroxy-5- (l-methylthiocyclopropyl) -2-cyclohexen-l-one

A mixture of 1.0 g (3.9 mmol) 3-hydroxy-5- (1-methyl-thiocyclopropyl) -2-propionyl-2-cyclohexen-l-one, 0.95 g (4.7 mmol) ( R) -0- [2- (4-chlorophenoxy) propyl] hydroxylamine and 80 ml of methanol were stirred for 24 hours and then concentrated under reduced pressure. The residue was taken up in tert-butyl methyl ether, after which the ether phase was extracted with 10% strength by weight sodium hydroxide solution. The aqueous phase was in turn extracted with tert-butyl methyl ether and then acidified with 10% by weight hydrochloric acid. Finally, the mixture was extracted again with tert-butyl methyl ether, after which the organic phase was dried over sodium sulfate and concentrated under reduced pressure. Yield: 59%; [α] _D 25 = - 13.1 (c = 1.0; in methanol);

² H NMR (200 MHz, in CDCI ₃ ): δ = 0.77 ppm (m, 2H); 0.97 ppm (m, 2H); 1.10 ppm (t, 3H); 1.35 ppm (d, 3H); 1.60 ppm (m, 1H); 2.13 ppm (s, 3H); 2.40 - 2.80 ppm (m, 4H); 2.90 ppm (q, 2H); 4.20 ppm (m, 2H); 4.60 ppm (m, 1H); 6.90 ppm (d, 2H); 7.20 ppm (d, 2H); 14.20 ppm (bs, 1H).

Prepress

(R) -0- [2- (4-chlorophenoxy) propyl] hydroxylamine

To a solution of 23.3 g (0.143 mol) of N-hydroxyphthalimide, 33.3 g (0.127 mol) of triphenylphosphine and 23.7 g (0.127 mol) of (R) -2- (4-chlorophenoxy) -l-propanol [ CAS Reg.No. 92471-63-1, Chem. Pharm.Bull ZI, 1955 (1985)] in 300 ml of tetrahydrofuran, 24.9 g (0.143 mol) of ethyl azodicarboxylic acid were slowly added dropwise. After a weakly exothermic reaction, the

Mixture stirred for about 15 hours and then concentrated. Chromatography of the residue on silica gel (cyclohexane / ethyl acetate 1: 1) gave 42 g of (R) -N- [2- (4-chlorophenoxy) propoxy] phthalimide.

This crude phthalimide product was then slowly mixed with 100 ml of ethanolamine. After 5 hours at 60 ° C., the reaction mixture was poured into ice water and extracted with Methylene chloride, washed the combined organic phases with water, dried over sodium sulfate and concentrated under reduced pressure. Yield: 81%; [α] r, 25 = -20.8 (c = 1.0; in methanol).

ⁱ HN R (360 MHz, in CDC1 ₃ ): δ = 1.25 ppm (d, 3H); 3.75 ppm (dd, 1H); 3.85 ppm (dd, 1H); 4.65 ppm (m, 1H); 5.50 ppm (bs, 2H); 6.90 ppm (d, 2H); 7.20 ppm (d, 2H).

The following Table 1 lists further optically active hydroxylamines III which were prepared or can be prepared in the same way. Tables 2 to 8 contain optically active cyclohexenone oxime ether I according to the invention.

Table 1

No. Xn phys. Date

(Rotation value [α] _D 25; c = 1.0 in CH ₃ OH / ⁱ H-MR [ppm])

-23.2 -20.8 -27.5 -26.2 -21.5

-27.5 Table 2

No . Rl R2 phys. Data (rotation value [α] _D 25; c = 1, 0, in CH ₃ OH /! H-NMR [ppm] / mp. [° C])

(RS) -2H-tetrahydropyran-3-yl -42.0

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -37,

(RS) -2H-tetrahydrothiopyran-3-yl -34,

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

(RS) -2H-tetrahydropyran-3-yl -33.6

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -38.9

(RS) -2H-tetrahydrothiopyran-3-yl-27,6

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

Phenyi

2,4,6-trimethylphenyl

4- (prop-2-ynyloxy) phenyl

4-fluoro-3-nitrophenyl

(RS) -2- (ethylthio) prop-l-yl

1-methylthiocycloprop-l-yl

1, 3-Dimethylpyrazol-5-yl

3-isopropylisoxazol-5-yl

(RS) -cyclohex-3-en-l-yl Table 3

No. R ¹ R2 phys. Data (rotation value [α] _D 25; c = 1.0, in CH ₃ OH / ^J -H-NMR [ppm] / mp. [° C])

(RS) -2H-tetrahydropyran-3-yl -13, 2 (R) -2H-tetrahydropyran-3-yl (S) -2H-tetrahydropyran-3-yl 2H-tetrahydropyran-4-yl -17.1

(RS) -2H-tetrahydrothiopyran-3-yl -11.8 (R) -2H-tetrahydrothiopyran-3-yl (S) -2H-tetrahydrothiopyran-3-yl (RS) -2H-tetrahydropyran-3-yl -11 , 7 (R) -2H-tetrahydropyran-3-yl (S) -2H-tetrahydropyran-3-yl 2H-tetrahydropyran-4-yl -12.5

(RS) -2H-tetrahydrothiopyran-3-yl - 8.3 (R) -2H-tetrahydrothiopyran-3-yl (S) -2H-tetrahydrothiopyran-3-yl phenyi -17.4

2, 4, 6-trimethylphenyl -15.6

4- (prop-2-ynyloxy) phenyi -14.9

4-fluoro-3-nitrophenyl -11.9

(RS) -2- (ethylthio) prop-l-yl -12.7 1-methylthiocycloprop-l-yl -14.9 1,3-dimethylpyrazol-5-y1 3-isopropylisoxazol-5-yl (RS) -cyclohex -3-en-l-yl -15.0

1-methylthiocycloprop-l-yl -15.1 Table 4

No . R ^l R2 phys. Data

(Rotation value

[α] _D 25; c = 1.0 in CH ₃ OH / iH NMR [ppm] / mp. [° C])

(RS) -2H-tetrahydropyran-3-yl -11.9

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -12.4

(RS) -2H-tetrahydrothiopyran-3-yl -10.3

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

(RS) -2H-tetrahydropyran-3-yl -10.8

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl ^* 8.9

(RS) -2H-tetrahydrothiopyran-3-yl -12.1

(R) -2H-tetrahydrothiopyran-3-yl

{S) -2H-tetrahydrothiopyran-3-y1

Phenyi -12.6

2,4,6-trimethylphenyl -13.0

4- (prop-2-ynyloxy) phenyi -13.0

4-fluoro-3-nitrophenyl - 8.1

(RS) -2- (ethylthio) prop-l-yl -11.5

1-methylthiocycloprop-l-yl -13.1

1,3-dimethylpyrazol-5-yl

3-isopropylisoxazol-5-yl

(RS) -cyclohex-3-en-l-yl

1-ethylthiocycloprop-l-yl - 9.7

1-ethylthiocycloprop-l-yl -12.3 No. R ¹ R ² physical data

(Rotation value [α] _D 25; c = 1.0, in CH ₃ OH /

^: H-NMR [ppm] / mp. [° C])

4.26 n-propyl 1-propylthiocycloprop-l-yl - 9.1 4.27 ethyl 1-propylthiocycloprop-l-yl -12.6

Table 5

No . Ri R2 phys. Date

(Rotation value

[α] _D 25; c = 1.0 in CH ₃ OH / ⁱ H NMR [ppm] / S p. [° C])

(RS) -2H-tetrahydropyran-3-yl -36.5

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -35.5

(RS) -2H-tetrahydrothiopyran-3-yl -25.3

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

(RS) -2H-tetrahydropyran-3-yl -32.5

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -34.2

(RS) -2H-tetrahydrothiopyran-3-yl -22.2

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

Phenyi

2,4,6-trimethylphenyl

4- (prop-2-ynyloxy) phenyi

4-fluoro-3-nitrophenyl

(RS) -2- (ethylthio) prop-1-yl

1-methylthiocycloprop-l-yl

1, 3-Dimethylpyrazol-5-yl

3-isopropylisoxazol-5-yl

(RS) -cyclohex-3-en-l-yl Table 6

Rl R2 phys. Data (rotation value [α] _D 25; c = 1.0, in CH3OH / iH-NMR [ppm] / mp. [° C])

(RS) -2H-tetrahydropyran-3-yl -26.5

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -16.3

(RS) -2H-tetrahydrothiopyran-3-yl -17.1

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-y1

(RS) -2H-tetrahydropyran-3-yl -24.7

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -24.9

(RS) -2H-tetrahydrothiopyran-3-yl -19.0

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

Phenyi

2,4,6-trimethylphenyl

4- (prop-2-ynyloxy) phenyl

4-fluoro-3-nitrophenyl

(RS) -2- (Ethyl lthio) prop-1-yl

1-methylthiocycloprop-l-yl

1, 3-Dimethylpyrazol-5-yl

3-isopropylisoxazol-5-yl

(RS) -cyclohex-3-en-l-yl Table 7

Rl R2 phys. Data (rotation value [α] _D 25; c = 1.0, in CH ₃ OH / ^X H-NMR [ppm] / mp. [° c])

(RS) -2H-tetrahydropyran-3-yl - 9.2

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl -13.2

(RS) -2H-tetrahydrothiopyran-3-yl -10.5

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

(RS) -2H-tetrahydropyran-3-yl - 6.6

(R) -2H-tetrahydropyran-3-yl

(S) -2H-tetrahydropyran-3-yl

2H-tetrahydropyran-4-yl

(RS) -2H-tetrahydrothiopyran-3-yl

(R) -2H-tetrahydrothiopyran-3-yl

(S) -2H-tetrahydrothiopyran-3-yl

Phenyi

2,4,6-trimethylphenyl

4- (prop-2-ynyloxy) phenyi

4-fluoro-3-nitrophenyl

(RS) -2- (ethylthio) prop-1-yl 1-methylthiocycloprσp-l-yl 1,3-dimethylpyrazol-5-yl 3-isopropylisoxazol-5-yl

(RS) -cyclohex-3-en-l-yl

1-methylthiocycloprop-l-yl

Table 8

No . R ⁱ R ^ phys. Data (rotation value [] _D 25; c = 1, 0 in CH ₃ OH / ^ H-NMR [ppm] / mp. [° C])

8.01 ethyl (RS) -2H-tetrahydropyran-3-yl -19.2 8.02 ethyl (R) -2H-tetrahydropyran-3-yl 8.03 ethyl (S) -2H-tetrahydropyran-3-yl 8.04 ethyl 2H-tetrahydropyran-4 -yl -19.1 8.05 ethyl (RS) -2H-tetrahydrothiopyran-3-yl -17.9 8.06 ethyl (R) -2H-tetrahydrothiopyran-3-yl 8.07 ethyl (S) -2H-tetrahydrothiopyran-3-yl 8.08 n-Propyl (RS) -2H-tetrahydropyran-3-yl -18.3 8.09 n-propyl (R) -2H-tetrahydropyran-3-yl 8.10 n-propyl (S) -2H-tetrahydropyran-3-yl 8.11 n -Propyl 2H-tetrahydropyran-4-yl 8.12 n-propyl (RS) -2H-tetrahydrothiopyran-3-yl 8.13 n-propyl (R) -2H-tetrahydrothiopyran-3-yl 8.14 n-propyl (S) -2H-tetrahydrothiopyran -3-yl 8.15 ethyl phenyi 8.16 ethyl 2, 4, 6-trimethylphenyl 8.17 ethyl 4- (prop-2-ynyloxy) phenyl 8.18 n-propyl 4-fluoro-3-nitrophenyl 8.19 n-propyl (RS) -2- ( Ethylthio) prop-l-yl 8.20 ethyl 1-methylthiocycloprop-l-yl 8.21 ethyl 1,3-dimethylpyrazol-5-yl 8.22 n-propyl 3-isopropylisoxazol-5-yl 8.23 n-propyl (RS) -cyclohex-3- en-l-yl 8.24 n-propyl 1-methylthiocycloprop-l-yl

The optically active cyclohexenone oxime ethers I are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides, in particular for combating plant species from the grass family (gramineae). In general, they are compatible and therefore selective in broadleaved crops and in monocotyledonous (monocotyledonous) crops which are not Gramineae. Some of the cyclohexenone oxime ethers I according to the invention are also suitable for the selective control of undesired grasses in Gramineae crops.

The optically active cyclohexenone oxime ether I or the herbicidal compositions comprising it can be, for example, in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or Granules by spraying, atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The compounds I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions. Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strongly polar solvents, such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. It can but also from active substance, wetting, adhesive, dispersing or emulsifying agents and possibly solvents or existing concentrates which are suitable for dilution with water.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and d-butylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributylphenylpolyglycol ether, alkylaryl alcohol, fatty alcohol alkyl alcohol polyether glycol, alkyl aryl alcohol ether, alcohol Condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite liquors or methyl cellulose are considered.

Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silica gel, silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. The formulations generally contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of such preparations are:

I. a solution of 90 parts by weight of compound no. 2.05 and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 20 parts by weight of compound no. 2.12, 80 parts by weight of xylene, 10 parts by weight of the

Addition product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the adduct and 40 moles of ethylene oxide with 1 mole of castor oil. By finely distributing the mixture in 100,000 parts by weight of water, a dispersion is obtained which contains 0.02% by weight of the active ingredient;

III. an aqueous dispersion of 20 parts by weight of compound No. 4.20, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. The mixture of this dispersion with 100,000 parts by weight of water contains 0.02% by weight of the active ingredient;

IV. An aqueous dispersion of 20 parts by weight of compound no. 4.12, 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct product of 40 mol ethylene oxide to 1 mol castor oil. The mixture of this dispersion with 100,000 parts by weight of water contains 0.02% of the active ingredient; V. a mixture ground in a hammer mill

80 parts by weight of compound no. 4.19, 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignam sulfonic acid from a sulfite liquor and 7 parts by weight of powdered silica gel. By finely distributing the mixture in 20,000 parts by weight of water, a spray broth is obtained which contains 0.1% by weight of the active ingredient;

VI. an intimate mixture of 3 parts by weight of compound no. 6.01 and 97 parts by weight of finely divided kaolin. This dusting agent contains 3% by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of compound no. 6.05, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffinol, which was sprayed onto the surface of this silica gel. This preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of compound no. 6.11, 10 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;

IX. a stable oily dispersion of 20 parts by weight of compound no. 6.12, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid urea -formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil;

X. A mixture, ground in a hammer mill, of 10 parts by weight of compound no. 2.01, 4 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 20 parts by weight of the sodium salt of a lignam sulfonic acid from a sulfite waste liquor , 38 parts by weight of silica gel and 38 parts by weight of kaolin. By finely distributing the mixture in 10,000 parts by weight Water gives a spray mixture which contains 0.1% by weight of the active ingredient.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit, if possible, while the active ingredients on the leaves growing below them unwanted plants or the uncovered floor area (post-directed, lay-by).

The application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1 kg / ha of active substance (a.S.) depending on the control target, season, target plants and growth stage.

In view of the versatility of the application methods, the optically active cyclohexenone oxime ethers I or agents containing them can also be used in a further number of crop plants for eliminating unwanted plants. The following crops are considered, for example:

Botanical name German name

Allium cepa kitchen onions 1

Ananas comosus Pineapple Arachis hypogaea peanut

Asparagus officinalis asparagus

Beta vulgaris spp. altissima beet

Beta vulgaris spp. rapa beet

Brassica napus var.napus rape Brassica napus var.napobrassica turnip

Brassica rapa var.silvestris beets

Camellia sinensis tea bush

Carthamus tinctorius Safflower - safflower

Carya illinoinensis pecan tree Citrus limon lemon

Citrus sinensis orange, orange

Coffea arabica (Coffea canephora, coffee

Coffea liberica) Cucumis sativus Cucumber Cynodon dactylon Bermudagras Daucus carota Carrot Elaeis guineensis Olpalme Fragaria vesca Strawberry Glycine max Soybean Gossypium hirsutum Cotton (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium Hummusakumumumumumum hospiceum Iumusumum hospice tree Iumusum hospice tree Iumusumum hospice tree Iumusum hospice tree culinaris lens Linum usitatissimum fiber small lycopersicon lycopersicum tomato Malus spp. Apple

Manihot esculenta Cassava Medicago sativa Alfalfa Musa spp. Fruit and flour banana

Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Phaseolus lunatus moon bean Phaseolus vulgaris bush beans Picea abies red spruce Pinus spp. jaw

Pisum sativum garden pea

Prunus avium sweet cherry

Prunus persica peach

Pyrus communis pear Ribes sylvestre red currant

Ricinus communis castor

Saccharum officinarum sugar cane

Seeale cereal rye

Solanum tuberosum potato sorghum bicolor (see vulgar) black millet

Theobroma cocoa cocoa tree

Trifolium pratense red clover

Triticum aestivum wheat Triticum durum durum wheat

Vicia faba horse beans

Vitis vinifera grapevine

Zea May's Corn

To broaden the spectrum of activity and to achieve synergistic effects, the optically active cyclohexenone oxime ethers I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, diazines, 4H-3, 1-benzoxazine derivatives, benzothiadiazinones, 2, 6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracil., Benzo hexane derivatives, come as mixing partners -l, 3-dione derivatives, which in

2-position e.g. bear a carboxy or carbimino group, quinoline carboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, aryloxy, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others are considered.

It may also be useful to apply the compounds I, alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling

Pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are used to correct nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

Examples of use

The herbicidal activity of the unsaturated cyclohexenone oxime ethers of the formula I was demonstrated by greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species. In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The vessels were lightly rained to encourage germination and growth and then covered with transparent plastic hoods until the plants had grown. This covering causes the test plants to germinate uniformly, provided that this has not been impaired by the active substances.

For the purpose of post-emergence treatment, the test plants were already grown in the test vessels or transplanted into the test vessels a few days beforehand. Depending on the growth habit, the active ingredients suspended or emulsified in water were only applied at a growth height of 3 to 15 cm. The application rate for post-emergence treatment was 0.06 and 0.03 kg / ha a.S.

The plants were kept at 10-25 ° C and 20-35 ° C depending on the species. The test period extended over 2 to 4 weeks. During this time, the plants were cared for and their reaction to the individual treatments was evaluated.

Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts, and 0 means no damage or normal growth.

The plants used in the greenhouse experiments are composed of the following types:

Latin name German name English name

Echinochloa crus-galli chicken millet barnyard grass Oryza sativa rice rice

Setaria italica millet foxtail millet

Setaria viridis green foxtail

With 0.06 or 0.03 kg / ha of active substance used in the post-emergence process, compounds 4.12 and 4.20 could be used to control undesirable grasses very well, while at the same time being compatible with the example culture of rice.

Claims

1. Mixtures of optically active cyclohexenone oxime ethers with R and S configuration in the oxime ether part of the general formula I

in which the substituents have the following meaning:

R ^{1 is} a Cχ-C ₆ alkyl group;

X is nitro, cyano, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ haloalkyl; n is 0 to 3 or 1 to 5 if all X is halogen; R ^{2 is} a Cχ-C ₄ -alkoxy-Cχ-C ₆ -alkyl- or Cχ-C -alkylthio-

Cχ-C ₆ alkyl group;

a C ₃ -C ₇ cycloalkyl group or a C ₅ -C cyclo alkenyl group, these groups optionally being able to carry one to three substituents selected from a group consisting of Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio, Cχ-C ₄ haloalkyl, Hydroxy1 and halogen;

a 5-membered saturated heterocycle which contains one or two oxygen and / or sulfur atoms as heteroatoms and which, if desired, can also carry one to three substituents, selected from a group consisting of Cχ-C-alkyl, Cχ-C ₄ -alkoxy, Cχ-C ₄ -alkylthio and Cχ-C ₄ -haloalkyl;

a 6- or 7-membered saturated or mono- or di-unsaturated heterocycle which contains one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as heteroatoms, where the heterocycle can optionally carry one to three substituents selected from a group consisting of hydroxyl, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cι-C ₄ alkylthio and Cι-C ₄ haloalkyl;

a 5-membered heteroaromatic containing one to three heteroatoms selected from a group consisting of one or two nitrogen atoms and one oxygen or sulfur atom, the heteroaromatic optionally being able to carry one to three substituents selected from a group consisting of halogen, cyano , Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy, Cχ-C ₄ alkylthio, Cχ-C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₃ alkenyloxy and C ₁ -C ₄ -Alkoxy- Cχ-C ₄ alkyl;

a phenyi or pyridyl group, these aromatics optionally being able to carry one to three substituents selected from a group consisting of halogen, nitro, cyano, Cχ-C ₄ alkyl, Cχ-C ₄ alkoxy,

Cχ-C ₄ alkylthio, Cχ-C ₄ haloalkyl, C ₃ -Cg alkenyloxy, Ö ₃ -C ₆ alkynyloxy and an amino group ~ NR ^a R ^b , wherein

R ^a for hydrogen, Cχ-C ₄ alkyl, C ₃ -Ce alkenyl or C ₃ -C ₆ alkynyl and

R is hydrogen, Cχ-C ₄ alkyl, C ₃ -C ₆ alkenyl,

C ₃ -Cs-alkynyl, Cx-Cς-acyl or benzoyl, which, if desired, can itself carry one to three residues, selected from a group consisting of nitro, cyano, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ -alkoxy, Cχ-C ₄ -alkylthio and Cχ-C ₄ -haloalkyl;

and the agriculturally useful salts and esters of Cχ-Cχo-carboxylic acids and inorganic acids of the compounds I,

with the proviso that the mixtures contain at least 75 mol% of isomers with R configuration in the oxime ether part.

2. Optically active cyclohexenone oxime ether I according to claim 1 with R configuration in the oxime ether part.

3. A process for the preparation of mixtures of optically active cyclohexenone oxime ethers I according to claim 1, characterized in that a cyclohexenone of the formula II

in a manner known per se in an inert organic solvent with a mixture of optically active hydroxylamines of the formula III

H Xn

H ₂ N OO CCHH ₂₂ CC 00 P (' ^Λ ) III

CH ₃

or reacted with a salt of the corresponding optically active hydroxylamine.

4. Herbicidal composition containing inert additives and a herbicidally effective amount of a mixture of optically active cyclohexenone oxime ethers I according to claim 1.

5. A method of controlling undesirable plant growth, characterized in that a herbicidally effective amount of a mixture of optically active cyclohexenone oxime ethers I as claimed in claim 1 is allowed to act on the plants, their habitat or their seeds.

6. Mixtures of optically active hydroxylamines with R and S configuration of the formula III

in the

X represents nitro, cyano, halogen, Cχ-C ₄ alkyl, Cχ-C ₄ haloalkyl;

and

n for 0 to 3 or 1 to 5 in the event that all X are halogen,

with the proviso that the mixtures contain at least 75 mol% of isomers with R configuration.

7. Optically active hydroxylamine III according to claim 6 with R configuration.

8. A process for the preparation of mixtures of optically active hydroxylamines of the formula III according to claim 5, characterized in that a mixture of optically active 2-phenoxypropyl compounds of the formula IV

in which L represents a nucleophilically substitutable leaving group, in the presence of a base with a cyclic hydroxyimide of the formula V

in which D represents C ₂ - or C ₃ -alkylene, C ₂ -alkenylene or a five- or six-membered ring which can be saturated or mono- to trisaturated and which, if desired, can contain a nitrogen atom as ring member,

implements and the process product VI

acidic or basic splits.

9. The method according to claim 8, characterized in that the optically active hydroxylamine III is released from the process product VI by means of ethanolamine.