DE4018508A1 - New cyclohexenone oxime phenyl- and hetero:aryl-alkynyl ether(s) - useful as herbicides, esp. for control of weed grasses - Google Patents

Abstract

Cyclohexenone oxime ethers (I) and their salts and 1-10C carboxylic acid and inorganic acid esters are new: where A = 3-6C alkynylene opt. mono-, di- or tri-substd. by 1-3C alkyl and/or halogen; Z = phenyl or an O, S or N-contg. 5- or 6-membered heteroaromatic gp. opt. substd. by Xn; X = nitro, cyano, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C haloalkyl, 1-4C haloalkoxy, carboxyl, 1-4C alkoxycarbonyl, benzyloxycarbonyl, and/or phenyl; where the rings are opt. mono-, di- or tri-substd. by nitro, cyano, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C haloalkyl, 1-4C haloalkoxy, carboxyl, 1-4C alkoxycarbonyl, and/or benzyloxycarbonyl; n = 0-3 or 1-5 when X = halogen; R1 = 1-6C alkyl; R2 = 1-4C alkoxy-1-6C alkyl, 1-4C alkylthio-1-6C alkyl, 3-7C cycloalkyl or 5-7C cycloalkenyl opt. mono-, di- or tri-substd. by 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C haloalkyl, hydroxy and/or halogen; a 5-membered satd. heterocyclic gp. contg. 1 or 2 O and/or S atoms and opt. mono-, di- or tri-substd. by 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio and/or 1-4C haloalkyl; a 6- or 7-membered heterocyclic gp. contg. 1 or 2 O and/or S atoms and up to 2 double bonds and opt. mono-, di- or tri-substd. by hydroxy, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio and/or 1-4C haloalkyl; a 5-membered heteroaromatic gp. contg. 1 or 2 N atoms and/or 1 O or S atom and opt. mono-, di- or tri-substd. by halogen, cyano, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C haloalkyl, 2-6C alkenyl, 2-6C alkenyloxy, 2-6C haloalkenyl and/or 1-4C alkoxy-1-4C alkyl; or phenyl or pyridyl opt. mono-, di- or tri-substd. by halogen, nitro, cyano, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, 1-4C alkoxy-1-4C alkyl, 1-4C alkylthio-1-4C alkyl, 1-4C haloalkyl, 3-6C alkenyloxy, 3-6C alkynyloxy. Intermediates of formula H2N-O-A-Z (III) are also claimed. USE - Cpds. (I) are herbicides, esp. against weed grasses. They can be applied at a rate of 0.001-3 kg/ha.

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 unsubstituted or substituted by 1 to 3 C₁-C₃-alkyl groups and / or halogen atoms C₃-C₆-alkynylene chain;
Z is phenyl, 5-membered or 6-membered heteroaromatic compound having one or more heteroatoms from the group consisting of oxygen, sulfur or nitrogen, where the aromatic radicals may be unsubstituted or substituted by n identical or different radicals X;
X is nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, carboxyl, C₁-C₄-alkoxycarbonyl, benzyloxycarbonyl and / or phenyl in which the aromatic radicals may carry one to three of the following substituents: nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkyloxy, Carboxyl, C₁-C₄-alkoxycarbonyl and / or benzyloxycarbonyl;
n is 0 to 3 or 1 to 5 in the case where X represents halogen atoms;
R² is a C₁-C₄-alkoxy-C₁-C₆-alkyl or C₁-C₄-alkylthio-C₁-C₆-alkyl group;
a C₁-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, C₁-C₄-haloalkyl, 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 C₁-C₄-haloalkyl,
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 C₁-C₄-haloalkyl,
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, C₁-C₄-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, C₂-C₆-haloalkenyl and / or C₁-C₄-alkoxy-C₁-C₄-alkyl,
a phenyl group or a pyridyl group, which group may carry one to three of the following substituents: halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₃- C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₄-alkoxy-C₁-C₄-alkyl and / or -NR³R⁴, wherein
R³ is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group and
R⁴ 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 one to three of the following substituents: nitro, cyano , Halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or C₁-C₄-haloalkyl
mean,
and their agriculturally useful salts and esters of C₁-C₁₀ carboxylic acids and inorganic acids.

Moreover, the invention relates to a method and intermediates their production and their use as plant protection products.

The cyclohexenones I according to the invention obviously have acidic properties 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 u. a.

• a) F benzyl and E 2-ethylthiopropyl (US Pat. No. 4,440,566);
• b) F benzyl, but-2-enyl and E a substituted 5-membered one Heteroaryl radical (EP-A 238 021, EP-A 125 094);
• c) F is benzyl, but-2-enyl and E is a substituted phenyl (EP-A 80 301);
• d) F but-2-enyl and E a 5- to 7-membered heterocyclic ring with up to two O, S atoms and up to two double bonds (EP-A 218 233)
• e) F 4-phenylbutyl, 4-phenyl-but-2-enyl, 4-phenylbut-3-enyl and E den residues listed under a) to d) (older German application P 38 38 309)

mean, 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 Distinguish unwanted 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 125 094, EP-A 142 741, US-A 42 49 937, EP-A 137 174 and EP-A 177 913) and the corresponding hydroxylamines of the formula III (Houben-Weyl, 10/1 p. 1181 ff) are produced (EP-A 169 521).

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. As carbonates, bicarbonates, acetates, Alcoholates or oxides of alkali or alkaline earth metals, in particular Sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide. also For example, organic bases such as pyridine or tertiary amines can be used. The base, 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 the compounds I can be obtained by treating the 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 prepared 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 the formula VII

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 to produce the enol ester VIII used in the reaction of compounds of the formula VII with acid chlorides IX in the presence of bases and subsequently rearranged with certain imidazole or pyridine derivatives become (JP-OS 79/063 052).

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

The synthesis of the hydroxylamines III, in which A is a substituted or unsubstituted C₃-C₆ alkynylene bridge is carried out according to the following Reaction scheme according to literature methods (J. Med. Chem. 29, 1389 (1986); EP-A 131,302; J. Med. Chem. 24, 678 (1981); J. Chem. Ecol. 10, 1201 (1982)). Starting from aryl or hetaryl halides X by coupling with a 1, ω-alkynol XI, XIa in the presence of palladium catalysts (see Tetrahedron Lett., 50 (1975) 4467). The thus obtained Alkynol IVa is coupled with a cyclic hydroxyimide V.  

The link can be directly after the Mitsunobu variant (Synthesis 1981, 1; J. Med. Chem. 33, 187 (1990)) between the arylalkinol IVa and the cyclic hydroxyimide V or by transfer of the OH group of the Arylalkinol IVa into a leaving group X (eg halogen, O-mesylate,. and subsequent substitution of the leaving group by the hydroxyimide V to the Imidethern VI.

Compounds in which the triple bond is not in conjugation to the Aromatics or heteroaromatics, z. B. by reaction of a Arylalkylhalogenids XII with the dianion of a 1, ω-alkynol XI to arylalkynol IVc be implemented. The arylalkinol IVc can then be used directly again or via the intermediate IVd to the protected hydroxylamine derivative XIb, as described above.

The protected hydroxylamine derivative VI is reacted with a base, e.g. B. with 2-aminoethanol split to the free hydroxylamine III:  

scheme

with Hal = Cl, Br, I; X = Cl, Br, mesylate, tosylate; m = 1, 2, 3, 4; o, p = 1, 2, 3;
A = C₃-alkynylene

In the cyclic hydroxyimides D z stands. For phenylene, naphthylene, Pyridinylene, cyclopentylene, cyclohexylene or cyclohexenylene. For example the following substances are considered:

The reaction of compounds IVb and IVd with the hydroxyimides V becomes expediently carried out in the presence of a base. Are suitable in principle all bases which are capable of hydroxyimides V. deprotect without attacking the imid system. These are in particular the so-called non-nucleophilic bases. For example, be mentioned 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 tertiary amines. It can also mixtures of these bases can 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, diazobicyclooctane, diazobicycloundecane, 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 lacks additional benefits. 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 of the hydroxyimide VI to a nucleophilic Attack of the hydroxyl ions on the carbonyl function of the imide moiety submissions.

Expediently, the starting compounds VI are reacted with the hydroxyimides V in a solvent which is under the reaction conditions inert behaves. Advantageous solvents are z. B. 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 IVb, d 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 quaternary 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 IVb and IVd with the hydroxyimides V is generally 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 presented together with the base in the solvent and the starting material VI dosed to this solution. It may prove 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.  

In the reaction of alkynols IVa or IVc with a cyclic Hydroxyimid of the formula V, after Mitsunobu, also arise the cyclic imide ethers of the formula VI.

The coupling of the alcohols IVa, c to a hydroxyimide of the formula V takes place in the presence of a triarylphosphine derivative and an azodicarboxylic acid diester in an inert solvent (J. Med. Chem. 33, 187 (1990)). For reasons of cost, hydroxyimidimide V is preferably hydroxyphthalimide Commitment.

As a phosphine derivative z. B. triphenylphosphine for use and as Azodicarbonsäurediester is preferably used the diethyl ester.

Suitable solvents are aprotic organic solvents such. B. Diethyl ether, tetrahydrofuran, toluene and ethyl acetate.

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 known methods be 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 help of other bases such as aqueous mineral bases, with Amines, hydrazines, hydroxylamines or by means of aqueous acids 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.

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, 1,1-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 alkynyls such as prop-2-ynylene, but-2-ynylene, but-3-ynylene, pent-2-ynylene, pent-3-ynylene, pent-4-ynylene, hex-2-ynylene, hex-3-ynylene , Hex-4-ynylene, hex-5-ynylene, pent-2-yn-4-enylene, pent-4-yn-2-enylene, hex-2-yn-4-enylene, hex-2-yn-5 -enylen, hex-3-yn-5-enylene, hex-4-yn-2-enylene, hex-5-yn-2-enylene, hex-5-yn-3-enylene and by 1 to 3 methyl or ethyl radicals and / or fluorine or chlorine may be substituted; In the case of the unsaturated chains, both the cis and trans forms can occur. Particularly preferred are but-2-ynylene, but-3-ynylene and prop-2-ynylene;
Z is phenyl, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine. Preference is given to phenyl, thiophene, furan, thiazole, pyridine, pyrimides, particular preference to phenyl, thiophene and pyridine.
X is 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-methylpropoxy, 2-methylpropoxy and 1,1-dimethoxyethoxy, in particular methoxy, ethoxy, 1-methylethoxy and 1,1-dimethoxyethoxy,
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,
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 also nitro, cyano,
Benzoxycarbonyl and phenyl, wherein the aromatic radicals in turn may carry one to three of the following radicals: nitro, cyano, carboxyl, benzyloxycarbonyl, halogen as generally and in particular called X; 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.

Particular preference is given to these aromatic radicals unsubstituted or monosubstituted representatives.
n is 0, 1, 2 or 3, in particular 0, 1 and 2. In the case of several radicals X, the substituents may be identical or different.
R 2 is alkyl as mentioned under R 1, which may carry one of the alkoxy or alkylthio group mentioned under X preferably 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, where these rings contain 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 heteroatoms 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, 3-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-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-dimethyl 1-2-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, 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-butenyloxy, 1-ethyl-3-butene yloxy, 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-propynyloxy and 2-butynyloxy;
by C₁-C₄-alkoxy, as mentioned above in general and in particular at X, substituted C₁-C₄-alkyl as generally and in particular mentioned above at X, preferably methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, 1 Ethoxyethyl and 2-ethoxyethyl;
Amino which may carry one or two of the following radicals: alkyl as mentioned at X, in particular methyl and ethyl; Alkenyl as mentioned above, in particular 2-propenyl and 2-butenyl;
Alkynyl, such as ethynil, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 Methyl 3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1 Hexynyl, 2-hexynyl, 3-hexynyl, 4-alkynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-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, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1 Ethyl 3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, especially 2-propynyl and 2-butynyl and / or
Acyl such as acetyl, propionyl, butyryl, 2-methyl-2-propionyl, 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 benzoyl.

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

Table A

Table B

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. Set the application forms according to the purposes of use; they should in any case as possible the 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 possibly solvent 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, and of 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% by weight, 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. 3.2 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. 3.4 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 addition product 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. 3.4 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 the active ingredient No. 3.2 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. 3.4 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 the active ingredient No. 3.2 are with 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. 3.4 are mixed with a mixture from 92 parts by weight of powdered silica gel and 8 parts by weight 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. 3.2 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 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 can the compounds of the invention in a large number of Crop plants are used. Consider, for example following cultures:

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 rape 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 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 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 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, cyclohexenones, (hetero) - aryloxypropionic acids, their salts, esters and amides and others into consideration.

In addition, it may be useful to use the cyclohexenone derivatives of the formula I. or herbicidal compositions containing them 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 syntheses described below for the new hydroxylamines can be with appropriate modification of the starting compound for Recovery of other compounds of formula III use. The obtained Compounds are summarized in Tables 1 to 3.

PREPARATION 4- (4-fluorophenyl) -3-butynol (Ex 1.1)

100 g of 4-bromofluorobenzene is dissolved in 350 ml of triethylamine and successively with 1 g of bis (triphenylphosphine) palladium (II) chloride, 3.8 g Added copper (I) iodide and 8.7 g of triphenylphosphine. This mixture will heated to reflux, then added dropwise at this temperature (ca. 100 ° C) 43.4 g of 3-butynol within 20 min to. It will be another 5 h at this Stirred temperature. After cooling, the triethylamine is distilled off. The residue is taken up in methyl tert-butyl ether and water. The aqueous phase is repeated twice with methyl tert-butyl ether extracted, the combined organic extracts are successively with 1 N hydrochloric acid and washed with 10% sodium bicarbonate solution, over Dried sodium sulfate and concentrated on a rotary evaporator. After Distillation under high vacuum gives 80 g (86%) of the desired Connection.  

5-aminooxy-1- (4-fluorophenyl) -1-pentyne (Ex 2.6) N- (5- (4-fluorophenyl) -4-pentynyloxy) phthalimide (Ex. 1.10)

33.1 g (0.186 mol) of 5-hydroxy-1- (4-fluorophenyl) -1-pentyne are dissolved in 430 ml dry tetrahydrofuran. To this is added 33.4 g (0.205 mol) of N-hydroxyphthalimide and 53.8 g (0.205 mol) of triphenylphosphine. Within 2.5 hours is then added dropwise under temperature control (max 40 ° C) 35.7 g (0.205 mol) Diethyl azodicarboxylate too. It is stirred overnight at room temperature, concentrated Take the mixture in vacuo and take up with 300 ml of dichloromethane. It will twice with sodium carbonate solution and once with saturated saline washed. After drying and concentration, chromatography on silica gel cleaned. The eluent is initially dichloromethane / n-hexane used later, then pure dichloromethane.

It is thus obtained in a yield of 49 g (82% of the phthalimide with Mp 87-88 ° C.

250 MHz H-NMR (DMSO-d6):
δ (ppm) = 1.9-2.1 (m, 2H); 2.68 (t, 2H); 4.32 (t, 2H); 7.18 (t, 2H); 7.4-7.6 (m, 2H); 7.85 (s, 4H).

5-aminooxy-1- (4-fluorophenyl) -1-pentyne (Ex 2.6)

47.7 g (0.148 mol) of the phthalimide ether shown above are added in portions in a mixture of 68 ml of ethanolamine and 40 ml of dichloromethane. After stirring for 2 h at room temperature, a clear solution is formed. This is added to 300 ml of ice-cold saturated saline. The mixture is extracted three times with 100 ml of dichloromethane, the washed Once against combined organic phases with saline, dried and restricts.

The title compound is obtained as an oil. Yield: 27.1 g (95%)
250 MHz ¹H-NMR (CDCl₃):
δ (ppm) = 1.8-2.0 (m, 2H); 2.47 (t, 2H); 3.8 (t, 2H); 5.4 (broad s, 2 H); 6.9-7.1 (m, 2H); 7.3-7.45 (m, 2H).

1-aminooxy-4-phenyl-2-butyne (Ex 2.2) 1-bromo-4-phenyl-2-butyne (Ex. 1.8)

140.4 g (0.96 mol) of 4-phenyl-2-butyn-1-ol (manufactured according to G. Dupont, Bull. Soc, Chim. Fr., 1954, page 816) are added in 600 ml of dry Toluene, add 14.5 ml of pyridine and then dropwise 119.1 g (0.44 mol) Phosphorus tribromide within 2 h, the temperature does not exceed 50 ° C should rise. After stirring overnight at room temperature, pour 1000 ml of ice-water, the organic phase is separated off and the aqueous extracted several times with methyltert. butyl ether after. The combined organic Phases are then washed neutral. The crude product which after Drying and removal of the solvents in vacuo, is fractionated distilled.

Yield: 126 g with a purity according to GC of 93%
Bp .: 83-85 ° C at 0.3 mbar

N- (4-phenyl-2-butynyloxy) phthalimide (Ex. 1.9)

51.3 g (0.23 mol) of the 1-bromo-4-phenyl-2-butyne obtained above are added dropwise over 30 minutes to a mixture consisting of 230 ml of N-methylpyrrolidin-2-one, 3 g of potassium iodide, 37 g (0.23 mol) of N-hydroxyphthalimide and 20.6 g (0.15 mol) of potassium carbonate. The mixture is then stirred for 5 h at 60 ° C and overnight at room temperature, poured into 800 ml of ice water, the precipitated crystals are filtered off and washed thoroughly with water and isopropanol. After drying, 57 g (86%) of the title compound with a mp. Of 127-129 ° C.
250 MHz H-NMR (DMSO-d6)
δ (ppm) = 3.71 (t, 2H); 4.95 (t, 2H); 7.28 (s, 5H); 7.9 (s, 4H)

1-amino-oxy-4-phenyl-2-butyne (Ex 2.2)

28.7 g (0.099 mol) of the phthalimide ether prepared above are initially charged in 100 ml of ethyl acetate, and 6 g (0.099 mol) of ethanolamine are added dropwise. The mixture is stirred for 1.5 h at 30 ° C, cooled in an ice bath, the crystals are filtered off and the mother liquor is added to a solution of 8.9 g (0.099 mol) of oxalic acid in 130 ml of ethyl acetate. The title compound precipitates as oxalate. The crystals are filtered off with suction, washed with cold ethyl acetate and dried in vacuo.
Yield: 20.2 g (81%), mp 113-117 ° C
300 MHz 1 H NMR (DMSO-d6)
δ (ppm) = 3.7 (s, 2H); 4.39 (s, 2H); 7.2-7.4 (m, 5H); 10.5 (wide s)

Table 1

Table 2

H₂N-focuser

The procedure given in the synthesis example below was with appropriate modification of the starting compound for recovery other compounds of formula I used; the compounds obtained are listed in the following tables with physical data; Compounds without this information can be obtained from the corresponding substances build up in an analogous way. They leave because of their near structural Relationships with manufactured and tested compounds expect similar effect.

Manufacturing instructions for 2-1- (4- (4-fluorophenyl) -but-3-inyloximino) butyl-3-hydroxy-5-tetrahyd-ropyran- 4-yl-cyclohex-2-enone (Ex. 3.20)

4 g (15 mmol) of 2-butyryl-3-hydroxy-5-tetrahydropyran-4-yl-cyclohex-2-enone are dissolved in 60 ml of dry methanol and treated with 2.7 g (15 mmol) of 4- (4-fluorophenyl ) -but-3-inoxymine. The reaction mixture is stirred for 16 h at room temperature. The methanol is then removed in a water jet vacuum and the residue is chromatographed on silica gel with methylene chloride. This gives 5.2 g (81.2%) of the desired compound.

applications

The effect of the cyclohexenone derivatives of the formula I on plant growth can be demonstrated by greenhouse experiments:

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 pre-emergence 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 the compounds Nos. 3.2 and 3.4 undesirable grassy plants very well Combat, while good tolerability of the example culture Rice.

Claims (7)

1. Cyclohexenonoximether the general formula I. in which the substituents have the following meanings:
R¹ is a C₁-C₆ alkyl group;
A is an unsubstituted or substituted by 1 to 3 C₁-C₃-alkyl groups and / or halogen atoms C₃-C₆-alkynylene chain;
Z is phenyl, 5-membered or 6-membered heteroaromatic compound having one or more heteroatoms from the group consisting of oxygen, sulfur or nitrogen, where the aromatic radicals may be unsubstituted or substituted by n identical or different radicals X;
X is nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, carboxyl, C₁-C₄-alkoxycarbonyl, benzyloxycarbonyl and / or phenyl in which the aromatic radicals may carry one to three of the following substituents: nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkyloxy, Carboxyl, C₁-C₄-alkoxycarbonyl and / or benzyloxycarbonyl;
n is 0 to 3 or 1 to 5 in the case where X 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, C₁-C₄-haloalkyl, Hydroxy and / or halogen;
a 5-membered saturated heterocycle containing one or two oxygen and / or sulfur atoms as heteroatoms, and which can carry up to three of the following groups: C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or C₁-C₄ haloalkyl;
a 6- or 7-membered heterocycle containing one or two oxygen and / or sulfur atoms and up 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 C₁-C₄-haloalkyl,
a 5-membered heteroaromatic 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, C₁-C₄-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, C₂-C₆- haloalkenyl and / or C₁- C₄-alkoxy-C₁-C₄-alkyl;
a phenyl group or a pyridyl group, these groups being able to carry one to three of the following substituents: halogen, nitro, cyano, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₃- C₆-alkenyloxy, C₃-C₆-alkynyloxy, C₁-C₄-alkoxy-C₁-C₄-alkyl and / or -NR³R⁴, wherein
R³ is hydrogen, a C₁-C₄ alkyl group, a C₃-C₆ alkenyl group or a C₃-C₆ alkynyl group and
R⁴ 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 one to three of the following substituents: nitro, cyano , Halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio and / or C₁-C₄-haloalkyl,
mean,
and their agriculturally useful salts and esters of C₁-C₁₀ carboxylic acids and inorganic acids. 2. 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 IIIH₂N-OAZ (III) or a salt of the corresponding hydroxylamine. 3. A herbicide containing a compound of the formula I according to claim 1 and inert additives. 4. 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. 5. Hydroxylamines of the formula III H₂N-OAZ (III), in which A and Z have the following meaning:
A is an unsubstituted or substituted by 1 to 3 C₁-C₃-alkyl groups and / or halogen atoms C₃-C₆-alkynylene chain;
Z is phenyl, 5-membered or 6-membered heteroaromatic compound having one or more heteroatoms from the group consisting of oxygen, sulfur or nitrogen, where the aromatic radicals may be unsubstituted or substituted by n identical or different radicals X;
X is nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, carboxyl, C₁-C₄-alkoxycarbonyl, benzyloxycarbonyl and / or phenyl in which the aromatic radicals may carry one to three of the following substituents: nitro, cyano, halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkyloxy, Carboxyl, C₁-C₄-alkoxycarbonyl and / or benzyloxycarbonyl;
n is 0 to 3 or 1 to 5 in the case where X is halogen. 6. A process for the preparation of hydroxylamines of formula III, according to claim 5, characterized in that a compound of formula IV XAZ (IV), in which A and Z have the meaning mentioned in claim 6 and X is a nucleophilically displaceable leaving group , with a cyclic hydroxyimide of the formula V in which D is C₂- and C₃-alkylene, C₂-alkenylene or a five- or six-membered ring which may contain 1 to 3 double bonds and one nitrogen atom, in the presence of a base to give compounds of the formula VI reacted and released from the imidethanes VI hydroxylamines III by means of bases. 7. The method according to claim 7, characterized in that the Releasing hydroxylamine III from the imide ether VI by means of ethanolamine.