DE4033423A1 - Cyclohexenone-oxime-ester derivs. - Google Patents

Abstract

Cyclohexenone oxime ether derivs. of formula (I) and their agriculturally useful salts and esters of 1-10C carboxylic acids and inorganic acids are new. R1 = 1-6C alkyl; A = oot. 1-3C alkyl-substd. 3-6C alkylene or 4-6C alkenyl in which one CH2 gp. is replaced by O, S, SO, SO2 or N(Ra); Ra = H, 1-4C alkyl, 3-6C alkenyl or 3-6C alkynyl; Z = Ph, 5-membered heteroaromatic contg. 1-3 heteroatoms chosen from 3N, O or S or 4-membered heteroaromatic contg. 1-4N; X = NRaRb, NO2 CN, halogen, 1-4C alkyl, partially or completely halogenated 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, partially or completely halogenated 1-4C alkoxv, carboxyl, 1-4C alkoxy carbonyl, benzyloxycarbonyl or KPh; n= 0-3 or 1-5 if Z = halogen; Rb = as Ra or is 1-6C aryl or R2 = 1-4C alkoxy(1-6C)alkyl, 1-4Calkylthio(1-6C)alkyl, 3-7C cycloalkyl, 5-7C cycloalkenyl, a 5-membered heterocycle (contg. 1 or 2 heteroatoms chosen from O and S), a 6- or 7-membered satd., singly or double unsatd. heterocycle (contg. or 2 heteroatoms chosen from O and S and opt. mono-, di or tri-substd. by O, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C di or tri-substd. by OH, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio or partially or completely halogenated 1-4C alkyl), a 5-membered heteroaromatic (contg. 1-3 heteroatoms chosen from O and S and opt. mono-, di or tri-substd. by halogen, CN, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, oartially or completely halogenated 1-4C alkyl, 2-6C alkenyl, 2-6C alkenyloxy, partially or completely halogenated 2-6C alkenyl or 1-4Calkoxy(1-4C)alkyll, Ph or pyridyl.

Description

The invention relates to novel herbicidally effective cyclohexenone oxime ethers Formula I

in which the substituents have the following meanings:
R¹ is a C₁-C₆ alkyl group;
A is an optionally C₁-C₃-alkyl-substituted C₃-C₆-alkylene or C₄-C₆- alkenylene chain in which a methylene group by an oxygen, a sulfur atom, a sulfoxide, a sulfone group or -N (Ra) -, wherein
Ra is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group,
is replaced;
Z phenyl,
a 5-membered heteroaromatic compound having one to three nitrogen atoms and / or one oxygen or sulfur atom,
a 6-membered heteroaromatic having one to four nitrogen atoms;
X is an amino group -NRaR ^b , in which
Ra is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group and
R ^{b is} hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group, a C₃-C₆ alkynyl group, a C₁-C₆ acyl group or a benzoyl radical, wherein the aromatic ring may carry up to three of the following substituents: nitro, Cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or C₁-C₄-haloalkyl nitro, cyano, halogen, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl , C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁-C₄-alkoxy, carboxyl, C₁-C₄-alkoxycarbonyl, benzyloxycarbonyl, phenyl, wherein the aromatic radicals may carry one to three of the following substituents: nitro, Cyano, halogen, C₁-C₄-alkyl, partially or completely halogenated C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, partially or completely halogenated C₁-C₄alkoxy, carboxyl, C₁-C₄alkoxycarbonyl, benzyloxycarbonyl,
n is 0 to 3 or 1 to 5 in the case where Z is halogen;
R² is a C₁-C₄-alkoxy-C₁-C₆-alkyl or C₁-C₄-alkylthio-C₁-C₆-alkyl group;
a C₃-C₇-cycloalkyl group or a C₅-C₇-cycloalkenyl group, these groups being able to carry one to three of the following substituents: C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁- C₄-alkyl, hydroxy and / or halogen;
a 5-membered saturated heterocycle containing one or two oxygen and / or sulfur atoms as heteroatoms and which may carry one to three of the following groups: C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or partially or fully halogenated C₁-C₄-alkyl;
a 6- or 7-membered heterocycle containing one or two oxygen and / or sulfur atoms and one to two double bonds, which ring may carry one to three of the following substituents: hydroxy, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy C₁-C₄-alkylthio and / or partially or fully halogenated C₁-C₄-alkyl;
a 5-membered heteroaromatic compound containing one to two nitrogen atoms and one oxygen atom or one sulfur atom, which ring may carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, partially or fully halogenated C₂-C₆-alkenyl and / or C₁-C₄-alkoxy-C₁-C₄-alkyl;
a phenyl group or a pyridyl group, which groups may carry one to three of the following substituents: halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁-C₄- Alkyl, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy and / or -NRaR ^b , in which Ra and R ^{b have} the abovementioned meaning,
mean,
and their agriculturally useful salts and esters of C₁-C₁₀ carboxylic acids and inorganic acids.

The cyclohexenones I according to the invention obviously acidic Character, d. H. They can be simple reaction products such as salts of Form alkali or alkaline earth compounds or enol esters.

The compounds of formula I can exist in several tautomeric forms occur, all of which are covered by the claim.

In the literature, cyclohexenones of general formula I '

in the ua
- D benzyl and E 2-ethylthiopropyl (US-A 44 40 566);
- D is benzyl, but-2-enyl and E is a substituted 5-membered heteroaryl radical (EP-A 2 38 021, EP-A 1 25 094);
D is benzyl, but-2-enyl and E is a substituted phenyl (EP-A 80 301);
D but-2-enyl and E is a 5- to 7-membered heterocyclic ring having up to two O, S atoms and having up to two double bonds (EP-A 2 18 233)
means described as herbicides.

However, compounds are sought which are high at low application rate Have selectivity, d. H. fight unwanted plants without doing so to damage the crops.  

According to this task, the new cyclohexenone oxime ethers of Formula I found that is characterized by a good herbicidal action against unwanted Outstanding grasses. The compounds are broad-leaved Crops and some compatible with grassroots crops such as rice.

The cyclohexenones of the formula I can be in a conventional manner already known derivatives of the formula II (EP-A 80 301, EP-A-1 25 094, EP-A 1 42 741, US-A 42 49 937, EP-A 1 37 174 and EP-A 1 77 913) and the corresponding hydroxyamines of the formula III (Houben-Weyl, 10/1 p. 1181 ff) are produced (EP-A 1 69 521).

It is expedient to carry out the reaction in a heterogeneous phase in a solvent, at a sufficient temperature below about 80 ° C, in Presence of a base and uses the hydroxylamine III in the form its ammonium salt.

Suitable bases are, for. Carbonates, bicarbonates, acetates; alcoholates or oxides of alkali or alkaline earth metals, in particular sodium hydroxide, Potassium hydroxide, magnesium oxide, calcium oxide. In addition, you can organic bases such as pyridine or teritäre amines use find. The Base is, for example, in an amount of 0.5 to 2 mol equivalent added based on the ammonium compound.

Suitable solvents are, for example, dimethyl sulfoxide; alcohols such as methanol, ethanol and isopropanol; aromatic hydrocarbons such as Benzene and toluene; chlorinated hydrocarbons such as chloroform and dichloroethane; aliphatic hydrocarbons such as hexane and cyclohexane; Esters such as ethyl acetate and ethers such as diethyl ether, dioxane and Tetrahydrofuran. Preferably, the reaction is carried out in methanol Sodium hydrogencarbonate as base by.

The reaction is completed in a few hours. The destination connection can z. B. by concentration of the mixture, distribution of the residue in methylene chloride / water and distilling off the solvent under reduced Be isolated.  

But you can also directly for this reaction, the free hydroxylamine base, z. In the form of an aqueous solution; depending on used Solvent for the compound II gives a one- or two-phase Reaction mixture.

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 dichloroethane; Esters, such as ethyl acetate; Nitriles such as acetonitrile and cyclic ethers such as dioxane and tetrahydrofuran.

Alkali metal salts of compounds I can be prepared by treating the 3-hydroxy 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 obtained from the sodium salts in the usual way be prepared, as well as ammonium and phosphonium salts by means Ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds of type II can z. B. from the corresponding cyclohexane-1,3-diones of formula IV

in the
Y is hydrogen or methoxycarbonyl
be prepared by known methods (Tetrahedron Lett., 2491 (1975)).

It is also possible to use the compounds of formula II via the intermediate the enol ester to be used in the reaction of compounds of Formula IV with acid chlorides in the presence of bases and then rearranged with certain imidazole or pyridine derivatives become (JP-OS 79/0 63 052).

The compounds of the formula IV are obtained via a number of known Process steps starting from known precursors.

The synthesis of hydroxylamines III, in which A is an unsubstituted 3-oxabutylene bridge is carried out according to the following reaction scheme:

Y = leaving group, e.g. B. bromine.

VII is coupled with a cyclic hydroxyimide V and the resulting protected hydroxylamine derivative VI z. B. with 2-aminoethanol to the free Hydroxylamine II cleaved.

In the cyclic hydroxyimides V D z. B. for C₂-C₃-alkylene, C₂- Alkenylene or one with up to 3 double bonds and optionally 1 nitrogen atom-containing 5- or 6-ring, z. For phenylene, Pyridinylene, cyclopentylene, cyclohexylene or cyclohexenylene. For example the following substances are considered:

The reaction of the compounds VII with the hydroxylimides V is expediently in the presence of a base. Suitable are in principle all bases that are capable of deprotonating the hydroxyimides V without to attack the imid system. These are special the so-called non-nucleophilic ones Bases. Examples include mineral bases such as alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal bicarbonates, organic bases such as aliphatic, cycloaliphatic and aromatic teritiäre amines. It can also be mixtures of these bases be used.

As individual compounds, the following bases are given by way of example: Sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, Barium carbonate, the bicarbonates of these metals, trimethylamine, triethylamine, Tributylamine, ethyldiisopropylamine, N, N-dimethylaniline, 4-N, N- Dimethylaminopyridine, diazabicyclooctane, diazabicycloundecane, N-methylpiperidine, 1,4-dimethylpiperazine, pyridine, quinoline, bipyridine, phenanthroline. Preferably, the inexpensive bases are sodium and potassium carbonate.

The base will generally be in equivalent amounts to an excess of 5 equivalents based on the hydroxyimide. A higher one Surplus is possible but has no additional advantages. The usage a small amount of base is also possible. However, preference is given a base amount of 1 to 3, in particular of 1 to 2 equivalents, based on the hydroxyimide V used.

The use of nucleophilic bases, e.g. 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 Use amounts relative to the hydroxyimide V to give a nucleophilic Attack of the hydroxyl ions on the carbonyl function of the imide moiety submissions.

It is expedient to use the starting compounds VII with the hydroxyimides V in a solvent which is under the reaction conditions inert behaves. Advantageous solvents are z. Eg polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, Dimethyl sulfoxide, sulfolane and cyclic ureas. The amount of solvent is not critical in general.

The reaction of the starting compounds VII with the hydroxyimides V can also be carried out using the phase transfer catalysis. In In this case, two-phase solvent are preferred with water  Chlorinated hydrocarbons used. As phase transfer catalysts The quaternaries commonly used for such purposes are suitable 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, Verlag Chemie, Weinheim 1980. The phase transfer catalysts are suitably used in amounts of 1 to 10% by volume, preferably in amounts of from 3 to 5% by volume, based on the volume the reaction mixture used.

The reaction of the starting compounds VII with the hydroxyimides V is in general in the temperature range between 0 and 140 ° C, preferably between 20 and 100 ° C, in particular between 40 and 80 ° C, carried out. Conveniently, The procedure is such that the hydroxyimide V together submitted with the base in the solvent and the starting material VII to dosed this solution. It may prove to be beneficial if the Hydroxyimide at a lower temperature, for example at 0 to 50 ° C, added and the reaction mixture only after this addition to the actual reaction temperature is heated.

After completion of the reaction, the cooled reaction mixture is suitably mixed with water, wherein the hydroxylamine derivatives formed Separate VI as crystalline solids or as oils. The hydroxylamine derivatives obtained in this way may, if desired, be further purified by recrystallization or by extraction.

The hydroxylamine derivatives VI can be stored temporarily or immediately be converted into the hydroxylamine derivatives III with 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 cited therein Writings are described. Preferably, the method according to DE-A 36 15 973 applied, according to which the hydroxylamine derivatives III means Ethanolamine are released. The release of the hydroxylamine derivatives III with the aid of other bases such as aqueous mineral bases, with amines, Hydrazines, hydroxylamines or by means of aqueous acids is also possible.

From the reaction mixtures obtained by these methods, the Hydroxylamine derivatives III isolated by conventional work-up methods be, for example, by extraction or by crystallization. to Increasing the crystallization tendency of these hydroxylamine derivatives can often be beneficial in their salts with mineral acids or to convert organic acids. These are generally diluted Solutions of these acids reacted with the hydroxylamine derivatives, namely  expediently in equivalent amounts. The resulting hydroxylammonium salts like the hydroxylamine derivatives with free amino group can directly the herbicides of formula I are processed or even if desired to be stored.

The halides VII. Required for the synthesis of the new hydroxylamines III can be prepared by literature methods (DE-34 37 919, Tetrahedron Lett. 28 (1979) 2639).

With regard to the biological effectiveness, preference is given to cyclohexenones of the formula I in which the substituents have the following meanings:
R1 is alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1 , 2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 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, especially ethyl and propyl;
A alkylene or alkenylene in which a methylene group is replaced by an oxygen, a sulfur atom, a sulfoxide, a sulfone group or -N (Ra) -, as
3-oxapropylene, 3-azapropylene, 3-thiapropylene, 3-thiapropylene-3-oxide, 3-thiapropylene-3,3-dioxide, 3-oxybutylene, 3-azabutylene, 3-thiabutylene, 3-thiabutylene-3-oxide, 3-thiabutylene-3,3-dioxide, 4-oxabutylene, 4-azabutylene, 4-thiabutylene, 4-thiabutylene-4-oxide, 4-thiabutylene-4,4-dioxide, 4-oxabut-2-enylene, 4- Azabut-2-enylene, 4-thiabut-2-enylene, 3-oxapentylene, 3-azapentylene, 3-thiapentylene, 3-thiapentylene-3-oxide, 3-thiapentylene-3,3-dioxide, 4-oxapentylene, 4- Azapentylene, 4-thiapentylene, 4-thiapentylene-4-oxide, 4-thiapentylene-4,4-dioxide, 5-oxapentylene, 5-azapentylene, 5-thiapentylene, 5-thiapentylene-5-oxide, 5-thiapentylene-5, 5-dioxide, 5-oxapent-3-enylene, 5-azapent-3-enylene, 5-thiapent-3-enylene, 3-oxahexylene, 3-azahexylene, 3-thiahexylene, 3-thiahexylene-3-oxide, 3 Thiahexylene-3,3-dioxide, 4-oxahexylene, 4-azahexylene, 4-thiahexylene, 4-thiahexylene-4-oxide, 4-thiahexylene-4,4-dioxide, 5-oxahexylene, 5-azahexylene, 5-thiahexylene, 5-thiahexylene-5-oxide, 5-thiahexylene-5,5-dioxide, 6-oxahexylene, 6-azahexylene, 6-thiahexylene , 6-thiahexylene-6-oxide, 6-thiahexylene-6,6-dioxide, 6-oxahex-4-enylene, 6-azahex-4-enylene, 6-thiahex-4-enylene. Particularly preferred are 3-oxapropylene, 3-oxabutylene and 4-oxabutylene.
Ra hydrogen;
Alkyl such as methyl, ethylene, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, especially methyl and ethyl;
Alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 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-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 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-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,2-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3 butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, esp other 2-propenyl and 2-butenyl;
Alkynyl, such as 2-propynyl, 2-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1- Dimethyl 2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1- Dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, especially 2-propynyl and 2-butynyl.
Z phenyl,
5-membered heteroaryl such as furanyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, in particular furanyl and thienyl,
6-membered heteroaryl such as pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, tetrazyl, in particular pyridyl and pyrimidyl;
X Nitro, Cyano,
Halogen such as fluorine, chlorine, bromine and iodine, in particular fluorine and chlorine;
Alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, in particular methyl and 1,1-dimethylethyl,
Alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methlypropoxy, 2-methylpropoxy and 1,1-dimethylethoxy, in particular methoxy, ethoxy, 1-methylethoxy and 1,1-dimethylethoxy,
Alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, in particular methylthio and ethylthio,
Haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- Dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, in particular difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and pentafluoroethyl,
Haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1, 1,2-trifluoroethoxy and pentafluoroethoxy, in particular trifluoromethoxy,
carboxyl,
Alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, 1-methylethoxycarbonyl, butyloxycarbonyl and 1,1-dimethylethoxycarbonyl, in particular methoxycarbonyl, ethoxycarbonyl and 1,1-dimethylethoxycarbonyl, in particular methoxycarbonyl and benzyloxycarbonyl and phenyl, wherein the aromatic radicals in turn carry one to three of the following radicals may be: nitro, cyano, carboxyl, benzyloxycarbonyl, halogen as generally and in particular at X called; Alkyl as mentioned for R¹, in particular methyl, ethyl and 1-methylethyl; Alkoxy as mentioned above, in particular methoxy and ethoxy; Alkylthio as mentioned above, in particular methylthio; Haloalkyl as mentioned above, in particular trifluoromethyl; Haloalkoxy as mentioned above, in particular difluoromethoxy and trifluoromethoxy and / or alkoxycarbonyl as mentioned above, in particular methoxycarbonyl and ethoxycarbonyl.

An amino group -NRaR ^b :
Ra is hydrogen, alkyl, alkenyl and alkynyl as in A generally and in particular mentioned;
R ^{b is} hydrogen, alkyl, alkenyl and alkynyl as mentioned generally in Ra and in particular;
Acyl groups such as acetyl, propionyl, butyryl, 2-methylpropionyl, pentanoyl, 2-methylbutyryl, 3-methylbutyryl, 2,2-dimethylpropionyl, hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2,2-dimethylbutyryl, 2, 3-dimethylbutyryl, 3,3-dimethylbutyryl and 2-ethylbutyryl, especially acetyl and propionyl;
or a benzoyl radical, wherein the aromatic radical may carry one to three of the following radicals: nitro, cyano, carboxyl, benzyloxycarbonyl, halogen is generally and especially mentioned at X; Alkyl as mentioned for R¹, in particular methyl, as mentioned above, in particular methoxy and ethoxy; Alkylthio as mentioned above, in particular methylthio; Haloalkyl as mentioned above, in particular trifluoromethyl; Haloalkoxy as mentioned above, in particular difluoromethoxy and trifluoromethoxy and / or alkoxycarbonyl as mentioned above, in particular methoxycarbonyl and ethoxycarbonyl.
n is 0, 1, 2 or 3, in particular 0, 1 and 2, in the case that Z is halogen also 1 to 5. Preferably, n is 0, 1 or 2. In the case of several radicals X, the substituents may be identical or different.
R 2 is alkyl as mentioned under X, and also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 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, which with one of the mentioned under X alkoxy or alkylthio preferred substituted in the 1-, 2- or 3-position, in particular 2-ethylthiopropyl;
5-membered heterocycloalkyl such as tetrahydrofuranyl, tetrahydrothienyl, dioxolanyl, dithiolanyl and oxathiolanyl, in particular tetrahydrofuranyl, tetrahydrothienyl and dioxolanyl, these rings having one to three of the C₁-C₄-alkyl groups already mentioned under X, C₁-C₄-alkoxy groups, C₁-C₄-alkylthio groups and / or C₁-C₄-haloalkyl groups,
5-membered heteroaryl such as pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, furanyl and thienyl, in particular isoxazolyl and furanyl,
a 6- or 7-membered heterocycle such as tetrahydropyran-3-yl, dihydropyran-3-yl, tetrahydropyran-4-yl, dihydropyran-4-yl, tetrahydrothiopyran-3-yl, dihydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, dihydrothiopyran 4-yl and dioxepan-5-yl, in particular tetrahydropyran-3-yl, tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl,
a phenyl or a pyridyl radical,
where the cyclic radicals may carry one to three of the alkyl groups mentioned under X, alkoxy groups, alkylthio groups and / or haloalkyl groups.

The 5-membered heteroaromatics in the meaning R² can carry as substituents the following radicals:
Halogen atom as mentioned under X, in particular fluorine and chlorine,
Alkoxyalkyl such as methoxymethyl, 2-methoxyethyl, 2-methoxypropyl, 4-methoxypropyl, 2-methoxy-1-methylethyl, ethoxymethyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 2-ethoxy-1-methylethyl and 1-ethoxy 1-methylethyl, especially methoxyethyl and ethoxyethyl,
Alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 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-dimethyl-1-butenyl, 1,2-dimeth yl-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-3-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, in particular 1-methylethenyl or corresponding alkenyloxy and / or haloalkenyl.

The 6- and 7-membered heterocycles may be in addition to the above substituents also carry hydroxyl groups.

In the case of the phenyl and pyridyl radicals, suitable substituents besides the abovementioned groups are also the following radicals:
Alkenyloxy such 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, 1,1-dimethyl-3-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-butenoxy, 1-ethyl-3-buteno xy, 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, especially 2-propenyloxy and 2-butenyloxy;
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-butynyloxy, 1-methyl-2-butynyloxy, 1,1-dimethyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexinyloxy, 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 2-propyynyloxy and 2-butynyloxy;
-NRaR ^b as in X in general and in particular.

Particularly preferred Cyclohexenonoximether of formula I are in the summarized in the following tables:

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

Table 14

Table 15

Table 16

Table 17

Table 18

Table 19

Table 20

Table 21

Table 22

Table 23

Table 24

Table 25

Table 26

Table 27

Table 28

Table 29

Table 30

Cyclohexenone oxime ethers I, where Z is the phenyl group, are quite particularly preferred.

The cyclohexenone derivatives I or the herbicidal compositions containing them For example, in the form of directly sprayable solutions, powders, Suspensions, including high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, Spreading agents or granules by spraying, misting, dusting, Scattering or pouring are applied. The application forms depend on the intended use; They should be possible in any case ensure the finest 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. As inert Additives come from mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and vegetable oils or of animal origin, aliphatic, cyclic and aromatic Hydrocarbons, eg. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, Butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or strong 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-dispersible granules by addition to be prepared from water. For the preparation of emulsions, pastes or oil dispersions may be the substrates as such or in an oil or Solvent dissolved by means of wetting, adhesion, dispersing or emulsifying agent be homogenized in water. It can also be more effective Substance, wetting, adhesion, dispersing or emulsifying agent and any solvents or oil existing concentrates are produced to Dilution with water are suitable.

As surface-active substances are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. As lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as fatty acids, alkyl and alkylaryl sulfonates, Alkyl, lauryl ether and fatty alcohol sulfates, as well as salts 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 the Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol,  Tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, Polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, Sorbitol esters, lignin-sulphite liquors or methylcellulose into consideration.

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

Granules, for. B. coated, impregnated and homogeneous granules be prepared by binding the active compounds to solid carriers. Solid carriers are mineral earths such as silicic acids, silica gels, silicates, Talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, Diatomaceous earth, calcium and magnesium sulphate, magnesium oxide, ground Plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products, such as cereal flour, tree bark, Wood and nutshell flour, cellulose powder or other solid Carriers.

The formulations contain between 0.1 and 95 wt .-%, preferably between 0.5 and 90% by weight of active ingredient. The active ingredients are in one Purity from 90% to 100%, preferably 95% to 100% (according to NMR spectrum) used.

The compounds I according to the invention can be, for example, as follows be formulated:

• I. Mix 90 parts by weight of compound no. 7.21 with 10 parts by weight of N-methyl-α-pyrrolidone and receives a solution, which is suitable for use in the form of very small drops.
• II. 20 parts by weight of compound no. 7.23 are in a mixture dissolved, consisting of 80 parts by weight of xylene, 10 parts by weight of Addition product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of Dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By Pour out and finely distribute the solution in 100 000 parts by weight Water gives an aqueous dispersion containing 0.02% by weight. of the active ingredient.  
• III. 20 parts by weight of compound no. 7.21 are in a mixture dissolved, consisting of 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles Ethylene oxide to 1 mole of isooctylphenol and 10 parts by weight of Addition product of 40 moles of ethylene oxide to 1 mole of castor oil consists. By pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion, containing 0.02% by weight of the active substance.
• IV. 20 parts by weight of drug no. 7.23 are in a mixture dissolved, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight a mineral oil fraction of boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and fine distribution The solution is obtained in 100 000 parts by weight of water aqueous dispersion containing 0.02 wt .-% of the active ingredient.
• V. 20 parts by weight of the active ingredient No. 7.23 are with 3 parts by weight the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight Water gives a spray mixture containing 0.1 wt .-% of the active ingredient contains.
• VI. 3 parts by weight of drug no. 7.15 are 97 parts by weight finely divided kaolin mixed. You get that way a dust containing 3% by weight of the active ingredient.
• VII. 30 parts by weight of compound no. 7.21 are mixed with a mixture from 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which is on the surface of this silica gel was sprayed, intimately mixed. You get on this Make a preparation of the drug with good adhesion.
• VIII. 20 parts by weight of the active substance No. 7.23 are with 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight Fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a Phenol-urea-formaldehyde condensates and 68 parts by weight a paraffinic mineral oil intimately mixed. You get one stable oily dispersion.

The application of the agents can be pre-emergence or postemergence respectively. Are the active ingredients for certain crops less compatible, so also application techniques can be applied to which the herbicidal agents are sprayed with the help of sprayers be that the leaves of the sensitive crops if possible not be taken while the active ingredients on the leaves underneath growing unwanted plants or the uncovered soil surface (post-directed, lay-by).

The application rates of active ingredient are depending on the season, target plants and growth stage 0.001 to 3 kg / ha, preferably 0.01 to 2.0 kg / ha.

In view of the detectable activity spectrum for weed control, the Compatibility with crops or the desired influence of crops Growth of the same and in view of the variety of application methods For example, the compounds of the invention can be used in a large number of crop plants be used. For example, the following may be considered cultures:

Botanical name German name Allium cepa onion Pineapple comosus pineapple Arachis hypogaea Peanut Asparagus officinalis asparagus Avena sativa oats Beta vulgaris ssp. altissima sugar beet Beta vulgaris spp. rapa mangel Beta vulgaris spp. esculenta Red beet Brassica napus var. Napus rape Brassica napus before. napobrassica Turnip Brassica napus var. Rapa White turnip Brassica rapa var. Silvestris rape Camellia sinensis Teestrauch Carthamus tinctorius Safflower safflower Carya illinoinensis Pecan Citrus limon lemon Citrus maxima grapefruit Citrus reticulata tangerine Citros sinensis Orange, orange Coffea arabica (Coffea canephora, Coffea liberica) coffee Cucumis melo melon 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 Helianthus tuberosus Jerusalem artichokes Hevea brasiliensis Para rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potatoes Juglans regia walnut tree Lactuca sativa lettuce Lens culinaris lens Linum usitatissimum flax Lycopersicon lycopersicum tomato Malus spp. Apple Manihot esculenta manioc Medicago sativa alfalfa Mentha piperita peppermint Musa spp. Fruit and flour banana Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Panicum miliaceum Rispenhirse Phaseolus lunatus butterbean Phaseolus mungo Erdbohne Phaseolus vulgaris bush beans Pennisetum glaucum Perl or cattail millet Petroselinum crispum spp. tuberosum root parsley Picea abies Rotfichte Abies alba white fir Pinus spp. pine Pisum sativum garden pea Prunus avium sweet cherry

Botanical name German name Prunus domestica plum Prunus dulcis almond Prunus persica peach Pyrus communis pear Ribes sylvestre Red currant Ribes uva-crispa gooseberry Ricinus communis castor-oil plant Saccharum officinarum sugarcane Secale cereal rye Sesamum indicum sesame Solanum tuberosum potato Sorghum bicolor (see vulgare) sorghum Sorghum dochna sweet sorghum Spinacia oleracea spinach Theobroma cacao cacao Trifolium pratense Red clover Triticum aestivum wheat Triticum durum durum wheat Vaccinium corymbosum Cultivated blueberry Vaccinium vitis-idaea Preißelbeere Vicia faba horse beans Vigna sinensis (V. unguiculata) cowpea Vitis vinifera grapevine Zea mays Corn

To broaden the spectrum of action and to achieve synergistic Effects, the cyclohexenone derivatives of the formula I both with each other as well as with representatives of other herbicidal or growth-regulating Active ingredient groups are mixed and applied together. For example Diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, Halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, Uracils, benzofuran derivatives, quinolinecarboxylic acids, sulphonylurea derivatives, Cyclohexenones, (hetero) -aryloxypropionic acids, their Salts, esters and amides and others.

In addition, it may be useful to use the cyclohexenone derivatives of the formula I. or containing herbicidal agents alone or in combination with others Herbicides or even mixed with other crop protection products together with, for example, means to combat Pests or phytopathogenic fungi or bacteria. Of interest Furthermore, the miscibility with mineral salt solutions, which for the elimination of Nutritional and trace element deficiencies are used. It can too non-phytotoxic oils and oil concentrates are added.  

The procedure given in the Synthesis Examples below was with appropriate modification of the starting compound for recovery further hydroxylamines of the formula III and cyclohexenone oxime ethers of Formula I used; the compounds obtained are in the following Tables with physical data listed.

Synthesis Examples for the Preparation of Hydroxylamines III N- [2- (2-fluorobenzyloxy) ethoxy] phthalimide

To a mixture of 165 g (0.71 mol) of 1-bromo-2- (2-fluorobenzyloxy) ethane, 116 g (0.7 mol) of N-hydroxyphthalimide and 710 ml of N-methyl-2-pyrrolidinone Was added dropwise at 20-25 ° C within 1 h 108 ml of triethylamine. After 5 g at 60 ° C poured the cold reaction mixture into 2000 ml of ice water, sucked the Precipitate, washed with water and isopropanol and dried i. Vak. over phosphorus pentoxide 185 g (82%) of phthalimide ether, m.p. 62-64 ° C - 1 H-NMR (250 MHZ, d₆-DMSO): δ = 3.85 (m, 2H), 4.35 (m, 2H), 4.54 (s, 2H), 7.10-7.40 (m, 4H), 7.88 (s, 4H).

O- [2- (2-fluorobenzyloxy) ethyl] hydroxylamine

184 g (0.58 mol) of the phthalimide ether prepared above were portionwise added in 270 ml of ethanolamine. After 3 h at 60 ° C poured the cold reaction mixture in 1000 ml of ice water. The hydrolyzate was three times extracted with 800 ml of dichloromethane. The combined organic phases were sat. with 200 ml. Brine solution washed over magnesium sulfate dried and i. Vak. concentrated. 98 g (91%) of hydroxylamine. H-NMR (250 MHZ, CDCl₃): δ = 3.70 (dd, 2H), 3.85 (dd, 2H), 4.54 (s, 2H), 5.50 (bs, 2H), 7.00-7.50 (m, 4H).

Synthesis example for the preparation of cyclohexenone oxime ethers I 2- [1 - [[2- (2-fluorobenzyloxy) ethoxy] imino] butyl] -3-hydroxy-5- (2H-tetra- hydropyran-4-yl) -2-cyclohexen-1-one

A mixture of 4.0 g (10 mmol) 2-butyryl-3-hydroxy-5- (2H-tetrahydropyran- 4-yl) -2-cyclohexen-1-one and 2.6 g (14 mmol) of O- [2- (2-fluorobenzyloxy) ethyl] hydroxylamine in 100 ml of methanol was stirred for 24 h. One narrowed i. Vak. and chromatographed the crude product on 100 g of silica gel / column 30 × 4 cm. (Eluent: ether). 3.5 g (54%) cyclohexenone oxime ether. - 1 H-NMR (300 MHZ, CDCl₃): δ = 0.93 (t, 3H), 1.20-1.77 (m, 7H), 1.90 (m, 1H), 2.23 (m, 2H), 2.58 (m, 2H), 2.92 (m, 2H), 3.38 (t, 2H), 3.80 (m, 2H), 4.03 (m, 2H), 4.25 (m, 2H), 4.68 (s, 2H), 6.93-7.50 (m, 4H), 14.30 (s, 1H).  

Table A

H₂N-OAZX _n (III)

Table B

Table C

Table D

Table E

Table F

Table G

Table H

Table I

Table J

Table K

applications

The herbicidal action of Cyclohexenoximether of formula I was allowed by Greenhouse experiments show:

The culture containers were plastic flowerpots with loamy sand and about 3.0% humus as substrate. The seeds of the test plants were sorted sown separately.

In the case of preliminary treatment, those were suspended or emulsified in water Active ingredients directly after sowing by means of finely distributing nozzles applied. The jars were lightly rained to allow germination and growth promote and then covered with transparent plastic hoods, until the plants had grown. This cover causes a uniform Germination of the test plants, if not affected by the active substances has been.

For the post-emergence treatment, the test plants were changed according to Growth form only with a stature height of 3 to 15 cm with the in water treated suspended or emulsified active ingredients. The application rate for postemergence treatment was 0.25 kg / ha a. S.

The plants were species-specific at temperatures of 10-25 ° C or 20-35 ° C held. The trial period lasted for 2 to 4 weeks. During this time, the plants were maintained and their response to the individual treatments were evaluated.

The rating was based on a scale from 0 to 100. 100 means no Rising of the plants or complete destruction of at least the above ground Parts and 0 no damage or normal growth.

The plants used in the greenhouse experiments took off following types together:

With 0.25 kg / ha a. S. used postemergence, can be with Examples 7.21 and 7.23 undesirable grassy plants very well combat, while tolerating the example of rice culture.

Claims (5)

1. Cyclohexenonoximether the general formula I. in which the substituents have the following meanings:
R¹ is a C₁-C₆ alkyl group;
A is an optionally C₁-C₃-alkyl-substituted C₃-C₆-alkylene or C₄-C₆-alkenylene chain, in which a methylene group by an oxygen, a sulfur atom, a sulfoxide, a sulfone group or -N (Ra) -, wherein
Ra is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group,
is replaced;
Z phenyl,
a 5-membered heteroaromatic compound having one to three nitrogen atoms and / or one oxygen or sulfur atom,
a 6-membered heteroaromatic having one to four nitrogen atoms;
X is an amino group -NRaR ^b , in which
Ra is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group and
R ^{b is} hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group, a C₃-C₆ alkynyl group, a C₁-C₆ acyl group or a benzoyl radical, wherein the aromatic ring may carry up to three of the following substituents: nitro, Cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or C₁-C₄-haloalkyl or
Nitro, cyano, halogen, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or fully halogenated C₁-C₄-alkoxy, carboxyl, C₁-C₄- Alkoxycarbonyl, benzyloxycarbonyl, phenyl, where the aromatic radicals may carry one to three of the following substituents:
Nitro, cyano, halogen, C₁-C₄-alkyl, partially or fully halogenated C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or fully halogenated C₁-C₄-alkoxy, carboxyl, C₁-C₄- Alkoxycarbonyl, benzyloxycarbonyl;
n is 0 to 3 or 1 to 5 in the case where Z is halogen;
R² is a C₁-C₄-alkoxy-C₁-C₆-alkyl or C₁-C₄-alkylthio-C₁-C₆-alkyl group;
a C₃-C₇-cycloalkyl group or a C₅-C₇-cycloalkenyl group, these groups being able to carry one to three of the following substituents: C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁- C₄-alkyl, hydroxy and / or halogen;
a 5-membered saturated heterocycle containing one or two oxygen and / or sulfur atoms as heteroatoms and which may carry one to three of the following groups: C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or partially or fully halogenated C₁-C₄-alkyl;
a 6- or 7-membered heterocycle containing one or two oxygen and / or sulfur atoms and one to two double bonds, which ring may carry one to three of the following substituents: hydroxy, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy C₁-C₄-alkylthio and / or partially or fully halogenated C₁-C₄-alkyl;
a 5-membered heteroaromatic compound containing one to two nitrogen atoms and one oxygen atom or one sulfur atom, which ring may carry one to three of the following substituents: halogen, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁-C₄-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, partially or fully halogenated C₂-C₆-alkenyl and / or C₁-C₄-alkoxy-C₁-C₄-alkyl;
a phenyl group or a pyridyl group, which groups may carry one to three of the following substituents: halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, partially or completely halogenated C₁-C₄- Alkyl, C₃-C₆-alkenyloxy, C₃-C₆-alkynyloxy and / or -NRaR ^b , in which Ra and R ^{b have} the abovementioned meaning,
mean, and their agriculturally useful salts and esters of C₁-C₁₀ carboxylic acids and inorganic acids. 2. Cyclohexenoximether of formula I according to claim 1, wherein Z is the phenyl group means. 3. A process for the preparation of compounds of the formula I according to claim 1, characterized in that a corresponding cyclohexenone of the formula II in a conventional manner in an inert organic solvent with a hydroxylamine of the formula IIIH ₂ NOAZX _n (III) or a salt of the corresponding hydroxylamine. 4. A herbicide containing a compound of the formula I according to claim 1 and inert additives. 5. A method for controlling undesired plant growth, characterized that the unwanted plants and / or their Habitat with a herbicidally effective amount of a cyclohexenone derivative of the formula I according to claim 1 treated.