DE4204206A1 - MIXTURES OF OPTICALLY ACTIVE CYCLOHEXENONE OXIMETHERS, PROCESSES AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES - Google Patents

Abstract

Mixtures of optically active cyclohexenone oxime ethers, with an R and S configuration in the oxime ether section of formula (I) where R<1> = 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; R<2> = 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 -NR<a>R<b>; R<a> = H, alkyl, alkenyl or alkinyl and R<b> = H, alkyl, alkenyl, alkinyl, acyl or optionally substituted benzoyl; and their agriculturally usable salts, and esters of C1-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

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

in which the substituents have the following meanings:
R ^{1 is} a C ₁ -C ₆ alkyl group;
X is nitro, cyano, halo, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl;
n is 0 to 3 or 1 to 5 in the case that all X is halogen;
R ^{2 is} a C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl or C ₁ -C ₄ -alkylthio-C ₁ -C ₆ -alkyl group;
a C ₃ -C ₇ -cycloalkyl group or a C ₅ -C ₇ -cycloalkenyl group, which groups may if desired carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ alkylthio, C ₁ -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, may carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -C ₄ haloalkyl;
a 6- or 7-membered saturated or mono- or diunsaturated heterocycle which contains one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as heteroatoms,
the heterocycle optionally being able to carry one to three substituents selected from a group consisting of hydroxyl, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio and C ₁ - 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,
wherein the heteroaromatic radical can if desired carry one to three substituents selected from a group consisting of halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ - C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy and C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl;
a phenyl or pyridyl group, wherein these aromatics GE if desired, can carry one to three substituents selected from a group consisting of halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C _4- alkylthio, C ₁ -C ₄ -haloalkyl, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ -alkynyloxy and an amino group -NRaR ^b , in which
Ra is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl and
R ^{b is} hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₆ -acyl or benzoyl, which, if desired, may on its side carry one to three radicals, selected from the group consisting of nitro, cyano, halo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -C ₄ haloalkyl;
and the agriculturally useful salts and esters of C ₁ -C ₁₀ -carboxylic acids and inorganic acids of the compounds I,
with the proviso that the mixtures contain at least 75 mole percent of isomers of R configuration in the oxime ether moiety.

Moreover, the invention relates to a method for Her position of these compounds, their use as herbicides as well as herbicidal agents which these compounds as effective contain the same substances.

Furthermore, the invention relates to novel mixtures optically active hydroxylamines of R and S configuration of formula III

in which
X is nitro, cyano, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl and
n is 0 to 3 or 1 to 5 in the case where all X are halogen,
with the proviso that the mixtures contain at least 75 mol% of isomers of R configuration, and a process for the preparation of the intermediates III.

From the literature are already herbicidally effective cyclohexane dione of formula I '

where R ^c , R ^d and R ^{e are,} inter alia, the following meanings:

• US 44 40 566 (R ^c = ethyl, propyl, R ^d = benzyl, R ^c = 2-ethylthiopropyl);
• EP-A 2 38 021 and EP-A 1 25 094 (R ^c = ethyl, propyl; R ^d = benzyl, but-2-enyl; R ^e = substituted 5-membered heteroaryl radical);
• EP-A 80 301 (R ^c = ethyl, propyl, R ^d = benzyl, but-2-enyl, R ^e = substituted phenyl);
• DE-A 38 38 309 (R ^c = ethyl, propyl; R ^d = substituted 4-phenylbutylene or 4-phenylbutenylene radical; R ^e = substituted 5- to 7-membered heterocycle);
• EP-A 4 56 112 (R ^c = ethyl, propyl; R ^c = substituted 3-phenoxypropylene or 2-phenoxyethylene radical; R ^e = substituted 5- to 7-membered heterocycle).

The herbicidal properties of these compounds, esp particular with regard to their selectivity against grass weeds in grass like crops, but may be limited friedigen.

The invention therefore new mixtures of cyclohexenone oxime ethers with improved selectivity against weed grasses in based on grassy crops such as rice and corn.

Accordingly, the mixtures defined above were made optically active cyclohexenone oxime ethers I found. also herbicidal agents were found which ent ent. these mixtures hold.

The mixtures of optically active cyclohexenone oxime ethers I are available in a variety of ways, and preferably in known manner from already known cyclo hexenones of the formula II, (DE-A 38 38 309, EP-A 2 43 313, EP-A 4 56 112) and the corresponding mixtures of optical active hydroxylamines of the formula III (cf., EP-A 1 69 521):

Preferably, a suitable salt of the hydroxyl is used amine III, in particular their hydrochloride, and leads the Reaction in heterogeneous phase in an inert solvent by, for example, in dimethyl sulfoxide, in an alcohol such as methanol, ethanol and isopropanol, in an aromatic Hydrocarbon such as benzene and toluene, in one chlorinated hydrocarbon such as chloroform and 1,2-di chloroethane, in an aliphatic hydrocarbon such as Hexane and cyclohexane, in an ester such as ethyl acetate ester or in an ether such as diethyl ether, dioxane and Tetrahydrofuran.

The reaction is carried out in the presence of a base, wherein normally a base amount of about 0.5 to 2 moles of Aqui valent, based on the ammonium compound, is sufficient.

As bases come z. As carbonates, bicarbonates, acetates, Alcoholates or oxides of alkali or alkaline earth metals, especially sodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide. Furthermore, are organic Bases such as pyridine and tert. Amines such as triethylamine suitable. Preferably, the reaction is carried out in methanol with Natri Umhydrogencarbonat as a base by.  

A variant of the method is the implementation without base with the free hydroxylamine bases III, z. In Form of an aqueous solution to make; depending on used Solvent for the compound II is obtained on or biphasic reaction mixture.

Suitable solvents for this variant are, for example Wise alcohols such as methanol, ethanol, isopropanol and cyclo hexanol, 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.

Conveniently, the cyclohexenone II and the Mi of optically active hydroxylamines III or their Salts in about stoichiometric ratio, but can in some cases, a surplus of one or the other Component, to about 10 mol%, 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 completed in a few hours. The product can in the usual way, for. B. by concentration of the mixture, Distribution of the residue in methylene chloride / water and Ab distilling the solvent under reduced pressure, be isolated.

Special conditions regarding the pressure are not to be respect, think highly of; In general, therefore, one works at atmospheric pressure or under the autogenous pressure of the particular diluent.

Due to their acidic character, the optically active Cyclohexenone oxime ethers I Salts of alkali or alkaline earth metals tallverbindungen and form enol esters.  

Alkali metal salts of compounds I can be treated by treatment of 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 are obtained.

Other metal salts such as manganese, copper, zinc, iron, Calcium, magnesium and barium salts can be extracted from the sodium Salts are prepared in the usual way, as well Ammonium and phosphonium salts by means of ammonia, Phosphonium, sulfonium or sulfoxonium hydroxides.

The esters of compounds I are also conventional Available (see, for example, Organikum, VEB Deutscher Verlag Sciences, 17th edition, Berlin 1988, p. 405-408).

The new mixtures of optically active hydroxylamines III can be over a series of known process steps starting from known precursors:

L = a leaving group z. As halogen, such as chlorine, bromine and iodine or CH ₃ SO ₂ -O-.

Preferably, the optically active alkylation is coupled medium V {Tetrahedron Lett. 29, 5493 (1988); J. Org. Chem. 52, 3587 (1987); EP-A 1 72 719; EP-A 2 30 379; US 48 41 079}, if desired, but also the optically active carbinol IV {Chem. Pharm. Bull. 33, 1955 (1985)) according to the Mitsunobu Variant (Synthesis 1, 1981; J. Med. Chem. 33, 187 (1990)}, with a cyclic hydroxyimide VI and this cleaves obtained protected hydroxylamine derivative VII to the free optically active hydroxylamine III, z. B. with 2-aminoethanol.

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

For example, the following substances come into consideration:

The reaction of the optically active alkylating agent V with the hydroxyimides VI is expediently in the presence ei ner base performed. In principle, all bases are suitable, which are able to deprotonate the hydroxyimides VI, without attacking the imid system. These are in particular the so-called non-nucleophilic bases.

Examples include mineral bases such as alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metals hydrogenated carbonates, organic bases such as aliphatic, cycloaliphatic and aromatic tertiary amines. It can but also mixtures of these bases can be used.

As individual compounds, the following bases are exemplary listed: sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, the hydrogencar Bonate these metals, trimethylamine, triethylamine, tri butylamine, ethyldiisopropylamine, N, N-dimethylaniline, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane, diazabi cycloundecane, N-methylpiperidine, 1,4-dimethylpiperazine, Pyridine, quinoline, bipyridine, phenanthroline. Preferred are the cheap bases sodium and potassium carbonate.

The base is generally added in equivalent amounts up to an excess of 5 equivalents, based on the hydroxy imid, admitted. A higher excess is possible brings but usually no additional benefits. The Verwen A small amount of base is also possible. before However, a base quantity of 1 to 3, in particular, is added from 1 to 2 equivalents, based on the hydroxyimide VI 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 supply the base in equivalent amounts of the hydroxyimide VI to a nucleophilic Attack of the hydroxyl ions on the carbonyl function of the imide to prevent grouping.

It is expedient to use the optically active Alkylating agent V with the hydroxyimides VI in one Solvent, which is under the reaction conditions  inert behaves. Advantageous solvents are z. B. polar, aprotic solvents such as dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide, sulfolane and cyclic urine substances. The amount of solvent is generally not kri table.

The reaction of the optically active alkylating agent V with The hydroxyimides VI can also be obtained using the phases Transfer catalysis be carried out. In this case will be water phase two-phase solvent is preferred Chlorinated hydrocarbons used.

As phase transfer catalysts, the usual wise used for such purposes quaternary ammonium and Phosphonium salts, polyethylene glycols, polyethylene glycol ethers and crown ethers, as described, for. In Dehmlow et al., Phase Transfer Catalysis, pp. 37-45 and pp. 86-93, publisher Che , Weinheim 1980, are described.

The phase transfer catalysts are conveniently in Amounts of 1 to 10% by volume, preferably in amounts of 3 to 5 Vol%, based on the volume of the reaction mixture, turned puts.

The reaction of the optically active alkylating agent V with The hydroxyimides VI is generally carried out in Temperaturbe rich between 0 and 140 ° C, preferably between 2 and 100 ° C, especially between 40 and 80 ° C. It will be advantageous here Proceeded that the hydroxyimide VI together with the Base in the solvent and the alkylating agent V dosed to this solution. It may prove to be cheap he when the hydroxyimide is at a lower temperature, for example at 0 to 50 ° C, added and the reaction Mix only after this addition to the actual Reaction temperature is heated.

After completion of the reaction, the cooled reaction mixture expediently mixed with water, wherein the hydroxylamine derivatives VII formed as crystalline test particles or as oils. That way he hydroxylamine derivatives can, if desired, by  Recrystallization or further purified by extraction become.

The hydroxylamine derivatives VII can be intermediately gelated or immediately into the optically active hydroxylamines III with be transformed free amino group.

This conversion can according to known methods be carried out, as described for example in DE-A 36 15 973 and the publications cited therein. Be Preferably, the method according to DE-A 36 15 973 is applied, after the optically active hydroxylamines III means Ethanolamine were released. The release of the optical active hydroxylamines III using other bases such as aqueous mineral bases, with amines, hydrazines, hydroxyl Amines or by means of aqueous acids is also possible.

From the reaction mixtures obtained by these methods can the optically active hydroxylamines III by means of isolated processing methods, for example by extraction or by crystallization. To increase the crystallization tendency of these hydroxylamines III can be often beneficial to these in their salts with mineral transfer acid or organic acids. This will be in the general dilute solutions of these acids with the Hydroxylamine derivatives implemented, and conveniently in equivalent amounts. The resulting hydroxylammonium salts Like the optically active hydroxylamines III (with free Amino group) directly to the optically active cyclohexenone oxime ethers of formula I are further processed or also, if desired, stored.

The optical purity of intermediates III and Cy clohexenone oxime ether I depends on the optical purity of the used Carbinole IV or alkylating agent V from. he According to the invention, R-configured carbinols IV or R configured alkylating agent V used, with As high as possible optical purity, so that in the Preparation of optically active hydroxylamines III and the Optically active Cyclohexenonoximether I each Isomerenge be obtained mixtures whose proportion of isomers with R-Kon  figuration at 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 as mixtures of isomers in the preparation, with both E / Z isomer mixtures (position of the oxime ether relative to R ¹ ) and diastereoisomer mixtures being possible. If desired, the isomer mixtures can be prepared by the methods customary for this purpose, eg. B. by chromatography or by crystallization, are separated.

The optically active Cyclohexenonoximether I can in several be written in tautomeric forms, all of which Invention become.

The collective used in the definition of the substituents concepts

• - halogen,
• C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -haloalkyl,
• C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy,
• C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ -alkynyl, C ₃ -C ₆ -alkynyloxy,
• - C ₁ -C ₆ acyl

provide shortcuts 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 ver be branched. The haloalkyl parts may be the same or ver carry different halogen atoms.

In detail, for example

• - Halogen: fluorine, chlorine, bromine and iodine;
• C ₁ -C ₄ -alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
• C ₁ -C ₄ alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
• C ₁ -C ₄ -alkylthio: methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;
• - C ₁ -C ₄ -haloalkyl: fluoromethyl, difluoromethyl, tri fluoromethyl, 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-propylene, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propylene , 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2 Methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl 3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl , 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-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, 1-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, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-D imethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-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-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2- propenyl;
• - C₂-C₆ alkenyloxy: ethenyloxy and C₃-C₆ alkenyloxy as 2-propenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy, 1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy, 1-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-2-pentenyloxy, 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, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy, 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, 1-ethyl-1-methyl-2-propenyloxy and 1-ethyl-2-methyl-2-propenyloxy.

With regard to their herbicidal activity, preference is given to cyclohexenones of the formula I in which the variables have the following meaning:
R ^{1 is} C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pen-X

• - Nitro, Cyano,
• - Halogen, preferably fluorine, chlorine and bromine;
• - C ₁ -C ₄ alkyl, preferably methyl;
• C ₁ -C ₄ -haloalkyl, preferably difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl;

particularly preferred is halogen;
n is 0 to 3 or 1 to 5 in the case that all X is halogen; more preferably 0 to 3;
R ²

• a C ₁ -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-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, wherein the alkyl group is represented by C ₁ -C ₄ alkoxy, preferably methoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy or substituted by C ₁ -C ₄ -alkylthio, preferably methylthio and ethylthio, preferably in the 1-, 2- or 3-position;
  most preferred is 2-ethylthiopropyl;
• a C ₃ -C ₇ cycloalkyl group or a C ₅ -C ₇ cycloalkenyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl and cycloheptenyl, which groups may be unsubstituted or may carry one to three of the following substituents :
  C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -C ₄ haloalkyl; very particular preference is 1-methylthio-1-cyclopropyl;
• a 5-membered saturated heterocycle such as tetrahydrofuranyl, tetrahydrothienyl, dioxolanyl, dithiolanyl and oxathiolanyl, especially tetrahydrofuranyl, tetrahydrothienyl and dioxolanyl, said rings being unsubstituted or bearing one to three substituents selected from a group consisting of C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -C ₄ haloalkyl;
• a 5-membered heteroaromatic compound such as pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, furanyl and thienyl, in particular isoxazolyl and furanyl, where the 5-membered heteroaromatic may be unsubstituted or may carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -haloalkyl halo and C ₁ -C ₄ -alkoxy-C ₁ -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-1-methylethyl and 1 Ethoxy-1-methylethyl, preferably methoxyethyl and ethoxyethyl,
  C ₂ -C ₆ alkenyl, such as ethenyl and C ₃ -C ₆ alkenyl, preferably 1-methylethen-1-yl,
  C ₂ -C ₆ -alkenyloxy such as ethenyloxy and C ₃ -C ₆ -alkenyloxy, in particular 1-methylethen-1-yloxy,
• a 6- or 7-membered heterocycle of
  • a) can be saturated, for. Tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl and dioxepan-5-yl,
  • b) may be mono- or diunsaturated, z. Dihydropyran-3-yl, dihydropyran-4-yl, dihydrothio-pyran-3-yl and dihydrothiopyran-4-yl,
• wherein the heterocycles may be unsubstituted or may carry one to three substituents selected from a group consisting of hydroxyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ - C ₄ haloalkyl; very particular preference is given to tetrahydropyran-3-yl, tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl;
• a phenyl or pyridyl group, both unsubbed or may carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -haloalkyl, C ₃ -C ₆ -alkenyloxy, preferably 2-propenyloxy and 2-butenyloxy, C ₃ -C ₆ -alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2 propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butyloxy, 1-methyl-2-butynyloxy, 1,1-dimethyl-2-propynyloxy , 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy, 1-methyl-4-pentynyloxy, 2 Methyl 3-pentynyloxy, 2-methyl-4-pentynyloxy, 3-methyl-4-pentynyloxy, 4-methyl-2-pentynyloxy, 1,1-dimethyl-2-butynyloxy, 1,1-dimethyl-3-butynyloxy , 1,2-dimethyl-3-butynyloxy, 2,2-dimethyl-3-butynyloxy, 1-ethyl-2-butynyloxy, 1-ethyl-3-butynyloxy, 2-ethyl-3-butynyloxy and 1-ethyl-1 -methyl-2-propynyloxy, especially for example 2-propynyloxy and 2-butynyloxy; one of the three substituents on the phenyl or pyridyl ring may also be an amino group -NRaR ^b , wherein
  Ra for
  Hydrogen,
  C ₁ -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 for
  Hydrogen,
  C ₁ -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
  C ₁ -C ₆ acyl, such as acetyl, propionyl, butyryl, 2-methylpropionyl, 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-ethylbutyryl, preferably acetyl and propionyl,

or benzoyl, which may be unsubstituted or in turn may carry one to three radicals selected from a group consisting of nitro, cyano, halogen, preferably fluorine, chlorine and bromine, C ₁ -C ₄ alkyl, preferably methyl, C ₁ -C ₄ Alkoxy, preferably methoxy and ethoxy, C ₁ -C ₄ -alkylthio, preferably methylthio, and C ₁ -C ₄ -haloalkyl, preferably trifluoromethyl;
stand.

As salts of the compounds of formula I come farmer commercially useful salts, such as alkali metal salts, in particular the sodium or potassium salt, Alkaline earth salts, in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and ammonium, phosphonium, sulfonium or Sulfoxonium salts, for example ammonium salts, tetra alkylammonium salts, benzyltrialkylammonium salts, tri alkylsulfonium salts or trialkylsulfoxonium salts in Be costume.

Examples of esters of C ₁ -C ₁₀ -carboxylic acids are C ₁ -C ₆ -alkylcarboxylic acids, such as methylcarboxylic acid (acetic acid), ethylcarboxylic acid (propionic acid), propylcarboxylic acid (butyric acid), 1-methylethylcarboxylic acid (isobutyric acid), butylcarboxylic acid, 1-methylpropylcarbon acid, 2-methylpropylcarboxylic acid, 1,1-dimethylethylcarboxylic acid, pentylcarboxylic acid, 1-methylbutylcarboxylic acid, 2-methylbutylcarboxylic acid, 3-methylbutylcarboxylic acid, 1,1-dimethylpropylcarboxylic acid, 1,2-dimethylpropylcarboxylic acid, 2,2-dimethylpropylcarboxylic acid, 1 Ethylpropylcarboxylic acid, benzoic acid and halogen-substituted benzoic acids, hexylcarboxylic acid, 1-methylpentylcarboxylic acid, 2-methylpentylcarboxylic acid, 3-methylpentylcarboxylic acid, 4-methylpentylcarboxylic acid, 1,1-dimethylbutylcarboxylic acid, 1,2-dimethylbutylcarboxylic acid, 1,3-dimethylbutylcarboxylic acid, 2,2- Dimethylbutylcarboxylic acid, 2,3-dimethylbutylcarboxylic acid, 3,3-dimethylbutylcarboxylic acid, 1-ethylbutylcarboxylic acid, 2-ethylbutyl carboxylic acid, 1,1,2-trimethylpropylcarboxylic acid, 1,2,2-trimethylpropylcarboxylic acid, 1-ethyl-1-methylpropylcarboxylic acid and 1-ethyl-2-methylpropylcarboxylic acid.

Preparation Examples (R) -2- {1- [2- (4-chlorophenoxy) propyloxyimino] propyl} -3-hy droxy-5- (1-methylthiocyclopropyl) -2-cyclohexen-1-one

A mixture of 1.0 g (3.9 mmol) of 3-hydroxy-5- (1-methylthiocyclopropyl) -2-propionyl-2-cyclohexen-1-one, 0.95 g (4 7 mmol) (R) O- [2- (4-chlorophenoxy) propyl] hydroxylamine and 80 ml of methanol were stirred for 24 hours and then concentrated at 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 wt .-% hydrochloric acid. Finally, it 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);
¹ H-NMR (200 MHz, in CDCl ₃ ): δ = ppm 0.77 (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).

preliminary stage (R) -O- [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) (R) -2- (4-chlorophenoxy) -1-propanol [CAS Reg. 92 471-63-1, Chem. Pharm. Bull 33, 1955 (1985)] in 300 ml of tetrahydrofuran 24.9 g (0.143 mol) of azodicarboxylic acid were slowly added dropwise ethyl ester. After a weak exothermic reaction, the Mixture for about 15 hours and then stirred concentrated. By chromatography of the residue on silica gel (Cyclohexane / ethyl acetate 1: 1) gave 42 g (R) -N- [2- (4-chlorophenoxy) propoxy] phthalimide.

This phthalimide crude product was subsequently added slowly with 100 ml of ethanolamine. After 5 hrs. At 60 ° C, the reaction mixture was poured into ice water, extracted with methylene chloride, washed the combined organic phases with water, dried over sodium sulfate and concentrated under reduced pressure. Yield: 81%; (α) _d 25 = -20.8 (c = 1.0, in methanol);
¹ H-NMR (360 MHz, in CDCl 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).

In the following Table 1 are further optically active Hydroxylamines III listed in the same way have been made or can be produced. Tables 2 to 5 contain optically active cyclohexenone oxime according to the invention ether I.

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

The optically active cyclohexenone oxime ethers I are suitable, see above probably as mixtures of isomers as well as in the form of pure isomers ren, as herbicides, especially for controlling Pflan zenarten from the grass family (Gramineae). In general they are compatible with me and therefore selective in broad leaves trigen cultures as well as in monocotyledonous (monocotyledonous) Ge growths that do not belong to the Gramineae. Some of the Cyclohexenonoximether I according to the invention are also to se selective control of unwanted grasses in Gramineae suitable cultures.

The optically active cyclohexenone oxime ethers I or they herbicidal compositions containing, for example, in the form of directly sprayable solutions, powders, suspensions, also high-percentage aqueous, oily or other Suspen ions or dispersions, emulsions, oil dispersions, Pa , dusts, litter or granules by Ver spraying, misting, dusting, scattering or pouring be used. The application forms depend on the Uses; In any case they should be as possible ensures the finest distribution of the active compounds according to the invention Afford.

The compounds I are generally suitable for the preparation of directly sprayable solutions, emulsions, rest or oil dispersions. The inert additives are mineral oil rock of medium to high boiling point, such as kerosene or Diesel oil, coal tar oils and vegetable or vegetable oils of animal origin, aliphatic, cyclic and aromati cal hydrocarbons, eg. Toluene, xylene, paraffin, Te trahydronaphthalene, alkylated naphthalenes or their deri vate, methanol, ethanol, propanol, butanol, cyclohexanol, Cyclohexanone, chlorobenzene, isophorone or strongly polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Aqueous application forms can be prepared from emulsion concentrates, Dispersions, pastes, wettable powders or water-dispersed gierbaren granules prepared by the addition of water who the. For the preparation of emulsions, pastes or oil disperse The substrates can be used as such or in an oil or Solvent solved by means of wetting, adhesive, dispersing or Emulsifying agents are homogenized in water. It can  but also from effective substance, wetting, adhesive, dispersing or emulsifier and possibly solvent or oil be standing concentrates are prepared for dilution are suitable with water.

Surfactants are the alkali, alkaline earth, Ammonium salts of aromatic sulfonic acids, eg. Lignin, Phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, alkyl, lau Rylether- and fatty alcohol sulfates, and salts sulfated Hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naph thalin and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with Phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkyl phenol, tributylphenyl polyglycol ethers, alkylaryl polyethers alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates sate, ethoxylated castor oil, polyoxyethylene alkyl ethers or Polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin-sulphite liquors or methylcellulose in Be costume.

Powders, litter and dusts can be mixed or mixed together grinding the active substances with a solid carrier.

Granules, for. B. wrapping, impregnation and homogeneous granules can be obtained by binding the active substances to solid Carriers are produced. Solid carriers are Mineral earths such as silica gel, silicas, silica gels, Silicates, talc, kaolin, limestone, lime, chalk, bolus, Sol, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urine substances and herbal products, such as cornmeal, tree bark, wood and nutshell flour, cellulose powder or on these solid carriers.  

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, Wirk material. The active ingredients are thereby in a purity of 90% up to 100%, preferably 95% to 100% (according to NMR spectrum) used.

Examples of such preparations are:

• I. a solution of 90 parts by weight of the compound No. 2.05 and 10 parts by weight of N-methyl-α-pyrrolidone, suitable for use in the form of very small drops is;
• II. A mixture of 20 parts by weight of the compound No. 2.12, 80 parts by weight of xylene, 10 parts by weight of Addition product of 8 to 10 moles of ethylene oxide 1 mole of oleic acid N-monoethanolamide, 5 parts by weight Calcium salt of dodecylbenzenesulfonic acid, 5% by weight Parts of the adduct and 40 moles of ethylene oxide to 1 mole of castor oil. By finely distributing the Mixture in 100 000 parts by weight of water is obtained a dispersion, the 0.02 wt .-% of the active ingredient ent holds;
• III. an aqueous dispersion of 20 parts by weight of Ver Bond No. 4.20, 40 parts by weight of cyclohexanone, 30 Parts by weight of isobutanol, 20 parts by weight of the plant product of 40 moles of ethylene oxide to 1 mol 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 Ver Binding No. 4.12, 25 parts by weight of cyclohexanone, 65 Parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. The mixture of this dispersion with 100,000 parts by weight len water contains 0.02% of the active ingredient;  
• V. a milled in a hammer mill mixture 80 parts by weight of compound no. 4.19, 3 parts by weight the sodium salt of diisobutylnaphthalene-α-sulfone acid, 10 parts by weight of the sodium salt of a lignin sulfonic acid from a spent liquor and 7 parts by weight powdered silica gel. By fine distribution the mixture is obtained in 20,000 parts by weight of water a spray mixture containing 0.1 wt .-% of the active ingredient ent holds;
• VI. an intimate mixture of 3 parts by weight of the compound No. 6.01 and 97 parts by weight of finely divided kaolin. This dust contains 3 wt .-% active ingredient;
• VII. An intimate mixture of 30 parts by weight of the verb No 6.05, 92 parts by weight of powdered silica acid gel and 8 parts by weight of paraffin oil based on the Surface of this silica gel was sprayed. This preparation gives the active ingredient a good Adhesiveness;
• VIII. A stable aqueous dispersion of 40 parts by weight Compound No. 6.11, 10 parts by weight of sodium salts of phenosulfonic acid-urea-formaldehyde Condensates, 2 parts by weight of silica gel and 48 parts by weight Divide water that can be diluted further;
• 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 fat Alcohol polyglycol ether, 20 parts by weight of sodium salts of phenol sulfonic acid-urea-formaldehyde Condensates and 68 parts by weight of a paraffinic mineral oil;
• X. A milled in a hammer mill mixture of 10 Parts by weight of compound no. 2.01, 4 parts by weight the sodium salt of diisobutylnaphthalene-α-sulfone acid, 20 parts by weight of the sodium salt of a lignin sulfonic acid from a spent liquor, 38 parts by weight Silica gel and 38 parts by weight of kaolin. By Fine distribution of the mixture in 10,000 parts by weight  Water is obtained a spray mixture containing 0.1 wt.% Of the Contains active substance.

The application of the herbicidal agents or the active ingredients can be pre-emergence or postemergence. Are the active ingredients for certain crops less ver tolerable, application techniques may be used in which the herbicidal agents with the help of sprayers be sprayed so that the leaves of the delicate Crops are not taken if possible while the active ingredients are growing on the leaves underneath unwanted plants or the uncovered soil surface long (post-directed, lay-by).

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

Considering the versatility of the application methods For example, the optically active cyclohexenone oxime ethers I or they containing agents still in a further number of Kulturpl used for the removal of unwanted plants become. For example, the following cultures may be considered:

Botanical name German name Allium cepa onion Pineapple comosus pineapple Arachis hypogaea Peanut Asparagus officinalis asparagus Beta vulgaris spp. altissima sugar beet Beta vulgaris spp. rapa mangel Brassica napus var. Napus rape Brassica napus var. Napobrassica Turnip Brassica rapa var. Silvestris beets Camellia sinensis Teestrauch Carthamus tinctorius Safflower - safflower Carya illinoinensis Pecan Citrus limon lemon Citrus sinensis Orange, orange Coffea arabica (Coffea canephora, Coffea liberica) coffee   Cucumis sativus cucumber Cynodon dactylon Bermuda grass Daucus carota carrot Elaeis guineensis oil palm Fragaria vesca strawberry Glycine max Soybean Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflower Hevea brasiliensis Para rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potatoes Juglans regia walnut tree Lens culinaris lens Linum usitatissimum flax Lycopersicon lycopersicum tomato Malus spp. Apple Manihot esculenta manioc Medicago sativa alfalfa Musa spp. Fruit and flour banana Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Phaseolus lunatus butterbean Phaseolus vulgaris bush beans Picea abies Rotfichte Pinus spp. pine Pisum sativum garden pea Prunus avium sweet cherry Prunus persica peach Pyrus communis pear Ribes sylvestre Red currant Ricinus communis castor-oil plant Saccharum officinarum sugarcane Secale cereal rye Solanum tuberosum potato Sorghum bicolor (see vulgare) sorghum Theobroma cacao cacao Trifolium pratense Red clover Triticum aestivum wheat   Triticum durum durum wheat Vicia faba horse beans Vitis vinifera grapevine Zea mays Corn

To widen the spectrum of action and to achieve synergistic effects can be the optically active cyclo hexenone oxime ether I with numerous representatives of others herbicidal or growth-regulating active ingredient groups ge mixed and applied together. For example come as a mixing partner Diazine, 4H-3,1-Benzoxazinderi vate, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiocarbamates, halocarboxylic acids, triazines, Amides, ureas, diphenyl ethers, triazinones, uracils, Benzofuran derivatives, cyclohexane-1,3-dione derivatives, which are known in 2 position z. B. carry a carboxy or carbimino group, Quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides, Sulfonylureas, aryloxy, heteroaryloxyphenoxypropion acids and their salts, esters and amides and others in Be costume.

In addition, it may be useful to use compounds I alone or in combination with other herbicides also with mixed with other pesticides mixed bring, for example with means to combat Pests or phytopathogenic fungi or bacteria. From Interest is also the miscibility with mineral salt Solutions that help to eliminate food and footprints element defects are used. It can not either phytotoxic oils and oil concentrates are added.

applications

The herbicidal action of the unsaturated cyclohexenone oxime ether of the formula I could be by greenhouse experiments demonstrate.

The culture vessels were plastic flower pots with loamy Sand with about 3.0% humus as substrate. The seeds of the test plants were sown separately by species.  

In pre-emergence treatment, those suspended in water or emulsified active ingredients directly after sowing by means of fine applied spreading nozzles. The vessels were light be rains to promote germination and growth and then covered with transparent plastic hoods until the plants had grown. This cover causes a uniform Germinating the test plants, if not affected by the substances was impaired.

already dressed in the test vessels or a few days previously transplanted to the test vessels. The application of In water suspended or emulsified drugs took place depending on growth form only at a stature height of 3 to 15 cm. The application rate for postemergence treatment was 0.06 and 0.03 kg / ha a.S.

The plants were species specific at temperatures of 10-25 ° C and 20-35 ° C held. The trial period he stretched over 2 to 4 weeks. During this time wur the plants are cared for and their reaction to the individual treatments were evaluated.

The rating was based on a scale from 0 to 100. Be 100 indicates no emergence of plants or complete destruction at least the above-ground parts and 0 no damage or normal growth.

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

With 0.06 or 0.03 kg / ha of active substance post-emergence used, with the compounds no. 4.12 and 4.20 combat unwanted grasses very well, at the same time early compatibility for the example of rice.

Claims (9)

1. Mixtures of optically active cyclohexenone oxime ethers with R and S configuration in the oxime ether part of the general formula I my in which the substituents have the following meanings:
R ^{1 is} a C ₁ -C ₆ alkyl group;
X is nitro, cyano, halo, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl;
n is 0 to 3 or 1 to 5 in the case that all X is halogen;
R ^{2 is} a C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl or C ₁ -C ₄ -alkylthio-C ₁ -C ₆ -alkyl group;
a C ₃ -C ₇ -cycloalkyl group or a C ₅ -C ₇ -cycloalkenyl group, these groups optionally being able to carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ -C ₄ - Alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl, hydroxyl and halo;
a 5-membered saturated heterocycle which contains one or two oxygen and / or sulfur atoms as heteroatoms and which, if desired, may carry one to three substituents selected from a group consisting of C ₁ -C ₄ -alkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -C ₄ haloalkyl;
a 6- or 7-membered saturated or mono- or diunsaturated heterocycle which contains one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as heteroatoms,
wherein the heterocycle may optionally carry one to three substituents selected from a group consisting of hydroxyl, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio and C ₁ -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,
wherein the heteroaromatic, if desired, can carry one to three substituents selected from a group consisting of halogen, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkenyloxy and C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl;
a phenyl or pyridyl group, which aromatics may optionally carry one to three substituents selected from a group consisting of halogen, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -Alkylthio, C ₁ -C ₄ -haloalkyl, C ₃ -C ₆ -alkenyloxy, C ₃ -C ₆ -alkynyloxy and an amino group -NRaR ^b , in which
Ra is hydrogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkynyl and
R ^{b is} hydrogen, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₆ -acyl or benzoyl, which, if desired, may in turn carry one to three radicals selected from the group consisting of nitro, cyano, halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio and C ₁ -C ₄ -haloalkyl,
stand;
and the agriculturally useful salts and esters of C ₁ -C ₁₀ -carboxylic acids and inorganic acids of the compounds I,
with the proviso that the mixtures keep at least 75 mol% of isomers of R configuration in the oxime ether part. 2. Optically active cyclohexenone oxime ethers I according to claim 1 with R configuration in the oxime ether part. 3. A process for the preparation of mixtures of optically active Cyclohexenonoximethern I according to claim I, 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 or with a salt of the corresponding optically active hydroxylamines. 4. A herbicidal composition containing inert additives and a herbicidally effective amount of a mixture of optical active cyclohexenone oxime ethers I according to claim 1. 5. Method of controlling unwanted plants effective amount of a mixture of optically active cyclo hexenone oxime ethers I according to claim 1 on the plants, whose habitat or seed is allowed to act.   6. Mixtures of optically active hydroxylamines with R and S configuration of the formula III in the
X is nitro, cyano, halo, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl;
and
n is 0 to 3 or 1 to 5 in the case where all X are halogen,
with the proviso that the mixtures contain at least 75 mole percent of isomers of R configuration. 7. Optically active hydroxylamines III according to claim 6 with R-configuration. 8. A process for preparing 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 is 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 may be saturated or monosubstituted to triunsaturated and which may if desired contain a nitrogen atom as ring member, and reacts Process Product VI acidic or basic splits. 9. The method according to claim 8, characterized in that the optically active hydroxylamine III from Ver product VI releases by means of ethanolamine.