CS253731B2 - Herbicide and process for preparing active component - Google Patents

Description

wherein A is a 5-12 membered cycloalkyl group to which one or two oxirane or thiirane rings are uncondensed and which is optionally substituted with up to 4 methyl groups and bridged by an alkylene chain of up to 3 carbon atoms, R1 is hydrogen, methoxycarbonyl or cyano, R1 represents C1-C4alkyl and R1 represents C1-C3alkyl, C3-C4alkenyl or C3-C4haloalkenyl; halogen as substituents or represents a propargyl group, or salts thereof.

The present invention relates to a herbicidal composition based on cyclohexenone derivatives.

Furthermore, the present invention relates to a process for the preparation of these herbicidally active cyclohexenone derivatives.

It is already known to use cyclohexenone derivatives for controlling undesirable monocotyledonous weeds in dicotyledonous crop plants (cf. DE-A 2 439 104). Furthermore, DE-A 3 032 973 discloses cycloalkenyl substituted derivatives at the 5-position, which are also herbicidally active.

We have now found novel cyclohexenone derivatives of the general formula I

OH

R1 ° in which

A represents a cycloalkyl group having 5 to 12 ring members to which one or two oxirane or thiirane rings is fused and which is optionally substituted by up to four methyl groups and is bridged by an alkylene chain of at most 3 carbon atoms, represents a hydrogen atom, a methoxycarbonyl group or a cyano group, preferably a hydrogen atom,

R is C1-C4alkyl and is C1-C3alkyl, C3-C4alkenyl, C3-C4haloalkenyl and C1-C3halo as substituents or propargyl, as well as the salts of these compounds have a good herbicidal effect, preferably against species of the grass family (Gramineae). These compounds are selective in dicotyledonous crops as well as in monocotyledonous crops, which do not belong to the grass family (Gramineae).

Accordingly, the present invention provides a herbicidal composition which is characterized in that it contains, in addition to inert additives, 0.1 to 95% by weight of at least one cyclohexenone derivative of the aforementioned and defined general formula I or a salt thereof.

The compounds of formula I may exist in several forms, all of which are within the scope of this invention:

In formula (I), A represents a cycloalkyl group having 5 to 12 ring members, preferably 5 to 8 ring members, to which one or two non-fused two oxirane or thiirane rings are substituted and which is optionally substituted by up to 4 methyl groups and is bridged by an alkylene chain of not more than 3 carbon atoms, for example epoxycyklopentylovou group, an epoxycyclohexyl group, epoxycykloheptylovou group epoxycyklooktylovou group epoxycyklododecylovou group diepoxycyklododecylovou group epoxymethylcyklopentylovou group dimethylepoxycyklopentylovou group epoxymethylcyklohexylovou group dimethylepoxyoyklohexylovou group epoxytrimethylcyklohexylovou group epoxytetramethylcyklohexylovou group epoxybicykloheptylovou group , diepoxytrimethylcyclohexyl, epoxydimethylbicycloheptyl, epithiocyclopentyl, epithiooyclohexyl, epithiobicycloheptyl. Particularly preferred is a 3,4-epoxycyclopentyl group.

R in formula I represents straight or branched alkyl groups having 1 to 4 carbon atoms, preferably 2 or 3 carbon atoms, i.e. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl isobutyl, tert-butyl.

R ³ in formula I represents propargyl, C 1 -C 3 alkyl, C 3 or C 4 alkenyl or C 3 or C 4 haloalkenyl which may contain up to three halogen atoms as substituents, for example methyl ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, alkyl, 3-chloroprop-2-enyl, 2-chlorprop-2-enyl a 1,3-dichloroprop-2-enyl group and a 2,3,3-trichloroprop-2-enyl group.

Suitable salts of the compounds of formula (I) are those suitable for agricultural purposes, for example alkali metal salts, in particular sodium or potassium salts, alkaline earth metal salts, in particular calcium salts, magnesium salts or barium salts, manganese salts, copper salts, zinc or iron and ammonium, sulfonium and phosphonium salts.

According to the invention, the compounds of formula X can be prepared by reacting the tricarbonyl compounds of formula II

O

R ^{1 0} in which

2

A, R, and R are as defined above, with hydroxylamine derivatives of the general formula

R ³ 0 - NHjY in which * 3 ·

R is as defined above and

Y is an anion.

The reaction is conveniently carried out in a heterogeneous phase in an inert diluent at a temperature between 0 and 80 ° C or at temperatures between 0 ° C and the boiling point of the reaction mixture in the presence of a base. Suitable bases are, for example, alkali metal or alkaline earth metal carbonates, bicarbonates, acetates, alkoxides, hydroxides or oxides, in particular sodium, potassium, magnesium ... calcium. In addition, organic bases such as pyridine or tertiary amines can also be used.

Suitable diluents are, for example, dimethylsulfoxide, alcohols such as methanol, ethanol, isopropanol, benzene, and optionally chlorinated hydrocarbons such as chloroform, dichloroethane, hexane, cyclohexane, esters such as ethyl acetate, cyclic ethers such as dioxane, tetrahydrofuran. Mixtures of these diluents may also be used.

The reaction is complete after several hours, whereupon the reaction product can be isolated by concentrating the mixture, adding water and extracting with a non-polar solvent such as methylene chloride and distilling off the solvent under reduced pressure.

In addition, the compounds of the formula I can be obtained by reacting the compounds of the formula II with hydroxylamine derivatives of the formula

R ³ - nh ₂ wherein _r 3 is as defined above, in inert diluents at temperatures between 0 ° C and the boiling point of the reaction mixture, especially at temperatures between 15 and 70 ° C. Alternatively, the hydroxylamine can also be used in aqueous solution.

Suitable diluents for this reaction are, for example, alcohols such as methanol, ethanol, isopropyl alcohol, cyclohexanol, or chlorinated hydrocarbons such as hexane, cyclohexane, methylene chloride, toluene, dichloroethane, esters such as ethyl acetate, nitriles such as acetonitrile, cyclic ethers such as tetrahydrofuran.

The alkali metal salts of the compounds of formula (I) may be prepared by reacting the compounds with sodium or potassium hydroxide in an aqueous solution or in an organic solvent such as methanol, ethanol or acetone. Sodium alkoxides and potassium alkoxides can also serve as bases. '

Salts with other metals, such as salts of manganese, copper, zinc, iron, calcium, magnesium and barium, can be prepared from sodium salts by reaction with the appropriate metal chlorides in aqueous solution. Ammonium, sulfonium and phosphonium salts can be prepared by reacting compounds of formula I with ammonium hydroxides, sulfonium hydroxides or phosphonium hydroxides, optionally in aqueous solution.

The tricarbonyl compounds of formula II are novel compounds. They can be prepared from cyclohexane-1,3-diones of formula III, which may also exist in tautomeric forms of formulas IIIa and IIIb.

(III) (IIIa) (IIIb) in which:

A and R ³ have the meanings given above by methods known in the literature (Tetrahedron Letters, 29, 2,491 (1975)).

It is also possible to produce the novel compounds of the formula II via the intermediate enol esters which are formed in the reaction of the compounds of the formula III optionally as a mixture of isomers and which are rearranged in the presence of imidazole or pyridine derivatives (JP-A 63 052/1979).

As can be seen from the above, the tricarbonyl derivatives of formula II are valuable intermediates for the preparation of herbicidally active cyclohexenone derivatives of formula I.

The compounds of formula (III) are obtained by methods known from the literature, as shown in the following scheme:

a-ch = ch-c-ch ₃

H

H ₃ COOC O

1) KOH

2) HCl

The aldehydes of formula A-CHO may be obtained from the corresponding unsaturated aldehydes by methods known in the literature, and it may be necessary to protect the aldehyde function;

The oxirane derivatives can be obtained in a manner known per se by reacting the corresponding unsaturated aldehydes or aldehyde derivatives with peroxy compounds such as hydrogen peroxide, tert-butyl hydroperoxide, permetic acid, m-chloroperbenzoic acid or air oxygen.

Compounds with an epoxidic structure can also be synthesized by cleavage of hydrogen halide from 1,2-halohydrins.

Thiirane derivatives can be obtained either from the corresponding epoxides by reaction with thiocyanates or with thiourea, as described, for example, in J. Chem. Soc. 1946, 1050, or from the corresponding unsaturated derivatives by reaction with sulfur-permitting agents such as arylthiosulfenyl chlorides (Chemistry of Heterocyclic Compounds, vol. 42, p. 340). The above conversion methods may optionally be carried out at any stage of the synthesis.

The following examples illustrate the preparation of cyclohexenone derivatives of the general formula I. In the examples, the parts by weight are relative to parts by volume as kilograms per liter.

1 H-NMR spectra were performed in deuterochloroform as solvent using tetramethylsilane as internal standard. ¹ H-chemical shifts are always given in ppm. The following abbreviations are used for signal structure:

s = singlet d = doublet t = triplet q = quartet m = multiplet, strongest signal.

Example 1

3.5 parts by weight of 2-butyryl-5- (3,4-epoxycyclohexyl) cyclohexane-1,3-dione, 1.5 parts by weight of allyloxyammonium chloride and 1.2 parts by weight of sodium bicarbonate are stirred in 50 parts by volume of methanol for 16 hours. hours at room temperature. The solvent is then distilled off under reduced pressure, the residue is stirred in each case with 50 parts by volume of water and dichloromethane, the organic phase is separated, the aqueous phase is extracted once with 50 parts by volume of dichloromethane, the combined organic phases are dried over sodium sulfate and distilled off under reduced pressure. 2- (1-allyloxyiminobutyl) -5- (3,4-epoxycyclohexyl) -3-hydroxycyclohex-2-en-1-one (active ingredient No. 1) is obtained.

1 H-NMR Spectrum:

= 0.95 (t), 2.9 (q), 5.3 (m).

Example 2

3.5 parts by weight of 2-butyryl-5- (3,4-epoxycyclohexyl) cyclohexane-1,3-dione and 0.8 parts by weight of ethoxyamine are stirred in 100 parts by volume of methanol at room temperature for 16 hours. The solvent was then distilled off under reduced pressure, the residue was dissolved in dichloromethane, the solution was washed with 5% (w / w) hydrochloric acid solution and water, dried over sodium sulfate and the solvent was distilled off under reduced pressure. 2- (1-ethoxyimino) -5- (3,4-epoxycyclohexyl) -3-hydroxycyclohex-2-en-1-one (active (Compound No. 2)) was obtained.

1 H-NMR Spectrum:

= 1.3 (t), 3.2 (m), 4.1 (d).

EXAMPLE 3 parts by weight of 2- (1-propoxyiminobutyl) -5- (cyclohex-3-enyl) -3-hydroxycyclohex-2-en-1-one are dissolved in 100 parts by weight of dichloromethane and are stirred at 5-10 DEG C. for this solution. C was added dropwise 5.8 parts by weight of m-chloroperbenzoic acid (about 80%) in 100 parts by volume of dichloromethane. After one hour, the reaction was examined by thin layer chromatography (finished thin layer chromatography plates using silica gel 60, solvent system: cyclohexane / ethyl acetate 1: 1).

(If starting material is still present, additional m-chloroperbenzoic acid is added dropwise until the reaction is complete). Excess peracid is decomposed by shaking with sodium thiosulfate solution.

Then, the reaction mixture is extracted twice with half-saturated sodium bicarbonate solution and once with water, the organic phase is dried over sodium sulfate and the solvent is distilled off under reduced pressure. To give 2- (1-propoxyimino-2-butyl) -5- (3,4-epoxycyclohexyl) -3-hydroxy-cyclohex-2-en-l ^J-one (active ingredient no. 3).

1 H-NMR spectrum:

= 2.2 (m), 3.1 (mi, 4.0 (q)).

The compounds listed below were obtained in the same manner as described in Examples 1 to 3.

Effective Data

substance number AND R ¹ R ² R ^{3 1} H-NMR spectra 4 3,4-epoxy-1-methylcyclohexyl H n-propyl ethyl 0.85 2.9 (S), 1.3 (m) (t), 5 3,4-epoxy-1-methylcyclohexyl H n-propyl allyl 1.0 2.5 (t), 1.3 (m) (s), δ 3,4-epoxy-4-methylcyclohexyl H n-propyl ethyl 1.0 2.5 (t), 1.3 (m) (with) 7 3,4-epoxy-4-methylcyclohexyl H n-propyl allyl 8 3,4-epoxy-6-methylcyclohexyl H n-propyl ethyl 0.95 4.1 (t), 1.6 (q) (m), 9 3,4-epoxy-6-methylcyclohexyl H n-propyl allyl 0.9 4.55 (m) 2.9 (d) (d) 10 3,4-epoxy-6-methylcyclohexyl H n-propyl 3-chloro-

allyl (trans)

11 1,2-epoxy-2,6,6-trimethylcyclohexyl H n-propyl ethyl 1.40 (s), 2.9 (m) 4.1 (g) 12 1,2-epoxy-2,6,6-trimethylcyclohexyl H n-propyl ethyl 13 3,4-dimethyl-3,4-epoxycyclohexyl H n-propyl ethyl 0.95 (t), 1.35 (m) 4.10 (q) 14 3,4-dimethyl-3,4-epoxycyclohexyl H n-propyl allyl 15 Dec 1,2-epoxycyclooctyl H n-propyl ethyl 1.0 (t), L, 30 t 4.1 (q) 16 1,2-epoxycyclooctyl H n-propyl allyl 0.95 (t), 1.35 (s) 2.95 (m) 17 4,5-8,9-diepoxycyclododecyl H n-propyl ethyl 18 4,5-8,9-diepoxycyclododecyl H n-propyl allyl

Continuation table

Effective Data

substance number AND R ¹ R ² R ³ @ 1 H-NMR spectrum 19 Dec 3,4-epoxycyclopentyl H n-propyl ethyl 20 May 3,4-epoxycyclopentyl H n-propyl allyl 21 3,4-epoxycyclopentyl H n-propyl 3-chlorallyl (trance) 22nd 3,4-epoxycyclopentyl H n-propyl propargyl 23 • 3,4-epoxycyclopentyl H ethyl ethyl 24 5,6-epoxybicyclo [2.2.1] hept-2-yl H ethyl propargyl 25 5,6-epoxybicyclo [2.2.1] hept-2-yl H ethyl allyl 2.5 (m), 2.9 (m), 4.55 (d) 26 5,6-epoxybicyclo [2.2.1] hept-2-yl H ethyl ethyl 0.8 (d), 2.5 (m), 2.9 (m) 27 Mar: 5,6-epoxybicyclo [2.2.1] hept-2-yl H n-propyl 3-chloro- allyl (trance) 3.15 (d), 4.5 (d), 6.3 (m) 28 5,6-epoxybicyclo [2.2.1] hept-2-yl H n-propyl ethyl 1.3 (t), 2.9 (s), 4.1 (q) 29 5,6-epoxybicyclo [2.2.1] hept-2-yl H n-propyl allyl 1.0 (t), 2.5 (m), 4.5 (d) 30 5,6-epoxybicyclo [2.2.1] hept-2-yl H n-propyl propargyl 1.0 (t), 2.6 (m), 4.65 (s) 31 2,3-epoxycyclohexyl H n-propyl ethyl 32 2,3-epoxycyclohexyl H n-propyl allyl 33 3,4-epithiocyclohexyl H n-propyl ethyl • 0.95 (t), 2.90 (d) 3.15 m 34 3,4-epithiocyclohexyl H n-propyl allyl 35 5,6-epithiobicyclo [2.2.1] hept-2-yl H n-propyl ethyl 36 5,6-epithiobicyclo [2.2.1] hept-2-yl H n-propyl allyl 37 3,4-epithiocyclopentyl H n-propyl ethyl 38 3,4-epithiocyclopentyl H n-propyl allyl

Continuation table

Očinná

Data

substance AND R ¹ 3 R R ^{3 3} h “NMR number spectrum 39 3,4-epithiocyclopentyl H ethyl allyl 40 3,4-epithiocyclopentyl H ethyl ethyl 41 2,3-epithiocyclopentyl H ethyl ethyl 42 2 _t 3 epithiocyklopentyl H ethyl allyl 43 2,3-epithiocyclopentyl H n-propyl allyl 44 2,3-epithiocyclopentyl H n-propyl ethyl 45 2,3-epithiocyclopentyl H n-propyl 3-chlorallyl (trance) 46 2,3-epithiocyclohexyl H n-propyl ethyl 47 2,3-epithiocyclohexyl H n-propyl allyl 48 2,3-epithiocyclohexyl H ethyl ethyl 49 2,3-epithiocyclohexyl H ethyl allyl 50 4,5-epoxycyclooctyl H n-propyl ethyl 1,0 (t) 1.35 (t), 4.1 (q) 51 4,5-epoxycyclooctyl H n-propyl allyl 1,0 (t) 2.9 (m) 4.55 (d) 52 4,5-epoxycyclooctyl H ethyl ethyl 1.35 (t) , 2.9 (m) 4.1 (q) 53 4,5-epoxycyclooctyl H ethyl allyl 1.15 (t) , 2.9 (m), 4.5 (d) 54 4,5-epoxycyclooctyl H ethyl 3-chloro- 1.15 (t) , 2.9 (m), allyl 4.55 (d) (trance) 55 4,5-epoxycyclooctyl H ^from n-propyl 3-chloro- 0.95 (t) , 1.5 (m), allyl 4.55 (d) (trance) 56 4,5-8,9-diepoxycyclodecyl H ethyl ethyl 1.2 (t). 1.3 (m), 4.1 (q) 57 3,4-epoxy-6-methylcyclohexyl H ethyl ethyl 1.35 (t) , 2.9 (q),

4.1 (q)

Continuation table

Active substance A number

Data

3 1

@ 1 H-NMR spectra

58 3,4-epoxy-6-methylcyclohexyl H ethyl allyl 1.15 4,5 (t), (d) 2.9 (m), 59 2,6-dimethyl-3,4-epoxycyclohexyl H n-propyl ethyl 1.3 (t), 2.9 ( s), 4.1 (q) 60 2,6-dimethyl-3,4-epoxycyclohexyl H n-propyl1 3-chloro 1.15 (t), 2.8 (m) allyl 6.35 (m) (trance) 61 5,6-epoxybicyclo [2.2.1] hept-2-yl H ethyl 3-chloro- 1.15 (t), 2.5 (m), allyl (trance) 4.55 (d) 62 3,4-epoxycyclohexyl H ethyl ethyl 1.13 (t), 3.15 (m), 4.1 (q) 63 3,4-epoxycyclohexyl H ethyl allyl 1.15 (t), 2.85 (d) 4.55 (d) 64 3,4-epoxycyclohexyl H ethyl 3-chloro 1.1 (t), 2.85 (d) allyl (trance) 6.3 (d) 65 3,4-epoxy-2-methylcyclohexyl H n-propyl ethyl 1.6 (q), 3,2 ( s), 4.1 (q) 66 3,4-epoxy-2-methylcyclohexyl H n-propyl allyl 0.95 (t), 1.85 (m), 3.20 (with) 67 3,4-epoxy-2-methylcyclohexyl H ethyl ethyl 1.3 (t), 2.35 (m), 4.1 (q) 68 3,4-epoxy-2-methylcyclohexyl H ethyl allyl 2.4 (m), 4.6 (d), 6.0 (m) 69 3,4-epoxy-2-methylcyclohexyl H ethyl 3-chloro 1.15 (t), 2.9 (q), allyl 4.55 (d) (trance) 70 3,4-epoxycyclopenty1 H ethyl allyl 71 3,4-epoxycyclopentyl H ethyl 3-chlorallyl 72 4,5-epoxycycloheptyl H ethyl ethyl 73 4,5-epoxycycloheptyl H ethyl allyl

T and b υ 1 to continue

Active substance A number

Data

3 1

RRR ^J H-NMR spectra

74 4,5-epoxycycloheptyl H ethyl 3-chlorallyl (trance) 75 4,5-epoxycycloheptyl H n-propyl 3-chlorallyl (trance) 76 4,5-epoxycycloheptyl H n-propyl ethyl 77 4,5-epoxycycloheptyl H n-propyl allyl

The novel herbicidal compositions can be used, for example, in the form of direct sprayable solutions, powders, suspensions, even highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters or granulates and applied by spraying, fogging, dusting, sprinkling or watering. The application forms are entirely governed by the purpose of application. In any case, they are intended to ensure the finest possible distribution of the active compounds according to the invention.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, suitable fractions of mineral oil of medium to high boiling point, such as kerosene or diesel engine oil, as well as tar oils as well as vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons , for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents such as dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by the addition of water. To produce emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized with a wetting agent, adhesive, dispersant or emulsifier in water. However, concentrates consisting of the active ingredient, wetting agent, adhesive, dispersing or emulsifying agent and optionally a solvent or oil which are suitable for dilution with iodine may also be prepared.

Suitable surfactants are alkali metal, alkaline earth metal or ammonium salts of lignin sulphonic acid or phenol sulphonic acid, alkylarylsulphonates, alkyl sulphates, alkyl sulphonates, alkali metal dibutylnaphthalenesulphonate salts and alkaline earth metal salts, lauryl ether sulphate, sulphated fatty alcohols, salts alkali metal and alkaline earth metal acids, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfated naphthalene and derivatives of naphthalene with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and ethylene oxide, phenol and formaldehyde, phenol and formaldehyde , nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of meat alcohol with ethylene oxide %, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, dusts and dusts can be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredient to solid carriers. Solid carriers are mineral clays such as silica gel, silicas, silica, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomite, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics fertilizers such as ammonium sulfate, ammonium phosphate, ureas and plant products such as cereal meal, ground tree bark, wood meal and ground nut shells, powdered cellulose and other solid carriers.

The compositions according to the invention contain between 0.1 and 55% by weight, preferably between 0.5 and 90% by weight, of active ingredient.

Examples of compositions according to the invention:

Example I part by weight of Compound No. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone to give a solution which is suitable in the form of minimal drops for the actual application.

Example XI parts of Compound No. 2 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight. addition product of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.

Example III parts by weight of Compound No. 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an adduct of 7 moles of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol. castor oil. Pouring this solution into 100,000% water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example IV parts by weight of active ingredient No. 4 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol. 65 parts by weight of a mineral oil fraction boiling at 210 DEG-280 DEG C. and 10 parts by weight of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it yields an aqueous dispersion containing 0.02% by weight of the active ingredient.

EXAMPLE In parts by weight of active ingredient No. 6, it is well mixed with 3 parts by weight of diisobutylnaphthalene-alpha-sulfonic acid sodium salt, 17 parts by weight of sodium ligninsulfonic acid from sulphite waste liquors and 60 parts by weight of silica gel powder, and the obtained mixture hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of the active ingredient.

Example VI parts by weight of active ingredient No. 13 are mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

Example VII parts by weight of active ingredient No. 11 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, a formulation with good adhesion is obtained.

Example VIII parts of active ingredient No. 1 are thoroughly mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenol, urea and formaldehyde and 68 parts of paraffinic mineral oil.

A stable oil dispersion is obtained. ,

Application of the compositions according to the invention can be carried out pre-emergence or post-emergence. If the active substances are less well tolerated by some crop plants, application methods may also be used in which the herbicidal compositions are sprayed by spraying so that the leaves of sensitive crop plants remain as far as possible without spraying, while the active substances reach the leaves of undesirable plants which they grow beneath them or the uncovered soil surface (post-directed, lay-by).

Depending on the stage of growth, the amount of active substance applied is from 0.025 to 3 kg of active substance per ha, preferably from 0.05 to 0.5 kg of active substance per ha.

The effect of the novel herbicidal compositions on plant growth can be illustrated in the following greenhouse experiments:

300 ml of plastic pots are used as crops for cultivation of crops, which are filled with clayey sand soil containing about 3.0% humus as a substrate. The seeds of the test plants are sown separately by species. In the pre-emergence treatment, the active compounds are immediately applied to the soil surface. The active compounds are suspended or emulsified in water as a dispersing medium and sprayed by means of fine nozzles. The application rate is 3.0 kg of active substance per ha.

After application of these compositions, the containers are slightly sprinkled with water to accelerate germination. The containers are then covered with a transparent plastic sheet until the plants have grown. This covering allows for a uniform growth of the test plants, if not already influenced by the active substances.

For the purposes of post-emergence treatment, the test plants are grown according to the form of growth to a height of 3-15 cm before the test plants are treated. Soybean plants are grown in peat-enriched soil as a substrate. For the purposes of post-emergence treatment, either directly sown and grown plants in the same vessel are selected, or plants which have been first grown separately and transplanted a few days before treatment are used. The application rate for post-emergence treatment is 0.06 to 0.125 kg of active ingredient per ha. In post-emergence treatment, no covering is performed.

The containers with the test plants are placed in a greenhouse, with warmer parts of the greenhouse (20-35 ° C) being chosen for the more thermophilous plant species, and colder parts (10-25 ° C) for the plants with a milder climate. The experiment takes 2 to 4 weeks.

During this time, the plants are treated and their response to the individual treatments evaluated. The evaluation is carried out on a scale of 0 to 100. 100 means that the plants do not occur, or the complete destruction of at least above-ground parts of the plants.

The plants used for the greenhouse experiments were selected from the following species:

Common Feathergrass (Alopecurus myosuroides), Deaf oat (Avena fatua), Common oat (Avena sativa), Bloody dew (Digitaria sanguinalis), Hedgehog (Echinochloa crus-galli), Soya (Glycine max), Rye (Lolium multiflorum) , walnuts (Setaria italica), white mustard (Sinapis alba) sorghum (Sorghum halepense), sorghum (Sorghum bicolor), maize (Zea mays).

The following compounds, known from DE-A 3 032 973, were used as comparative agents:

2- (1-Allyloxyamino-n-butyl) -5- (cyclohex-1-en-4-yl) -3-hydroxycyclohex-2-en-1-one (A)

2- (1-ethoxyimino-n-butyl) -5- (cyclohex-1-en-4-yl) -3-hydroxycyclohex-2-en-1-one (B) as well as the following compounds known from DE- A 3 219 490:

2- (1-ethoxyamino-n-butyl) -5- (cyclooct-1-en-5-yl) -3-hydroxycyclohex-2-en-1-one (C), or compositions containing these compounds as active substances.

In pre-emergence applications, for example, compositions containing Compounds Nos. 4, 6, 11 and 13 as active ingredients have been shown to be herbicidally active against grass plants, while white mustard (Sinapis alba) as a representative of dicotyledonous plants remains completely undamaged.

The results of this test are summarized in Table 1 below.

Table 1

Herbicidal effect with pre-emergence application of 3 kg of active substance per hectare in a greenhouse

Active substance Test plants and% damage Sinapis number Avena ^K Lolium Echinochloa alba sativa multiflorum crus-galli

6 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 4 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 11 0 100 ALIGN! 100 ALIGN! 95 13 0 100 ALIGN! 100 ALIGN! 100 ALIGN!

* it is evaluated as an undesirable plant of fallen seeds

Furthermore, for example, the compositions containing compounds Nos. 4 and 6 show a strong herbicidal activity against a broad spectrum of weeds when applied at 0.125 kg of active substance per ha in post-emergence treatment; Soybean as a dicotyledonous plant remains intact.

The results of this test are summarized in Table 2 below.

Table2

Herbicidal effect with post-emergence application of 0.125 kg of active substance per ha in a greenhouse

Active substance Test plants and% damage Glycine Sorghum number * Zea * Setaria Alopecurus Avena Echinochloa max. Bicolor mays italica myosuroides fatua crus-galli

0 100 100 100 95 90 100

0 100 100 100 90 90 100 * evaluated as undesirable plants (from fallen sorghum and corn seeds)

By means of compositions which also contain Compounds Nos. 1 and 2a, which are also selected as examples, as active ingredients, problematic weed-type weeds can be controlled much better with complete soy tolerance than with the known comparative means A and B.

The results of this test are summarized in Table 3 below.

Table 3

Herbicidal effect with post-emergence application of 0.06 kg of active ingredient per ha in a greenhouse

Active substance Test plants and% damage number Glycine * Sorghum ** Setaria Digitaria Sorghum

max. bicolor italica sanguinalis halepense 2 0 95 98 90 95 (B) 0 60 65 10 10 1 * 0 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! AND 0 35 30 30 0 * at 0 125 kg / ha evaluates as undesirable plant from fallen seeds sorghum

By means of compositions comprising as active ingredient compounds 26, 28, 52, 54, 55 and 61, undesirable grass species can be controlled, while the broadleaf (dicotyledon) alfalfa plant (as an example of a crop plant) remains completely undamaged.

The results of this test are summarized in Table 4 below.

Table 4

Herbicidal effect in post-emergence application in a greenhouse

Effective substance amount of active ingredient used Trial plants and% damage Medicago Zea * Avena Echinochloa Setaria number kg / ha sativa mays fatua Crus Galli italica

28 0.125 0 100 ALIGN! 98 90 95 26 0.125 0 100 ALIGN! 98 95 100 ALIGN! 61 0.125 0 100 ALIGN! 98 100 ALIGN! 98 55 0.125 0 100 ALIGN! 95 95 100 ALIGN! 52 0.125 0 100 ALIGN! 95 95 100 ALIGN! 54 0.06 0 100 ALIGN! 90 98 100 ALIGN! * it is evaluated as an undesirable plant of fallen seeds maize

By way of example, the composition which contains Compound (8) as an active ingredient is already suitable for controlling undesirable monocotyledonous weeds and is well tolerated for wheat.

The results of this test are summarized in Table 5 below.

Table 5

Herbicidal effect in post-emergence application of 0.03 kg of active substance No. 8 per 1 ha (greenhouse experiment)

Active substance number

Test plants and% damage of Triticum Alopeourus Avena aestivum myosuroldes fatua

Setaria italica

In comparison with the known herbicidal composition C, for example, the herbicidal effect of a composition containing Compound No. 50 as active ingredient is significantly higher, without adversely affecting alfalfa tolerance.

The results of this test are shown in Table 6 below.

Table 6

Herbicidal effect with post-emergence application of 0.06 kg of active substance per ha in a greenhouse

Active substance Experimentally plants and% damage number Medicago Alopeourus Digitaria Echinochloa Sorghum sativa myosuroides sanguinalis Crus Galli halepense

0 98

C 0 60

90

70

Taking into account the efficacy spectrum for weed control, crop tolerance or undesirable growth of the number of application methods, the compounds of the invention can be used in a large number of crop plants.

For example, the following types of crop plants are suitable:

Botanical name Czech name Allium cepa onion Pineapple comosus pineapple Arachis hypogaea peanut Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. aitissima sugar beet Beta vulgaris spp. rapa fodder beet Beta vulgaris spp. esculenta beetroot Brassica napus var. napus rape Brassica napus var. napobrassica turnip Brassica napus var. rapa white beets Brassica rapa var. silvestris oilseed rape Camellia sinensis tea Carthamus tinctorius Safflower Carya illinoinensis walnut pecan Citrus limon lemon tree Citrus maxima lemon tree Citrus retículata tangerine Citrus sinensis orange Coffea arabica coffee tree (Coffea canephora) Cucumis melo melon Cucumis sativus cucumber Cynodon dactylon troskut Daucus carota carrot Elaeis guineensis coconut tree Fragaria vesca Strawberry Glycine max soya Gossypium hirsutum cotton (Gossypium arboreum, Gossypium herbaceum, bsypium vitifolium) r; ianthus arinuus sunflower relianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potato Juglans regia walnut Lactuca sativa lettuce Lens culinaris edible lentils Linum usitatissimum only Lycopersicon lycopersicum tomato Malus spp. apple tree Manihot esculenta tapioca Medicago sativa vojtějška Metha piperita peppermint Musa spp. banana tree Nicotiana tabacum (N. rustica) tobacco

Botanical name

Olea europaea

Oryza sativa

Panicum miliaceium

Phaseolus lunatus

Phaseolus mungo

Phaseolus vulgaris

Pennisetum glaucum

Petroselinum crispum spp. tuberosum species Pioea abies Abies alba Pinus spp.

Pisum sativum

Prunus avium

Prunus domestica

Prunus dulcis

Prunus persica

Pyrus oommunis

Ribes sylvestre

Rlbes uva-crispa

Riclnus oommunis

Saccharum officinarum

Secale cereale

Sesanum indicum

Solanum tuberosum

Sorghum bicolor (Sorghum vulgare)

Sorghum dochna

Spinacia oleracea

Theobroma cacao

Trifolium pratense

Triticum aestivum

Vacoinium corymbosum

Vaccinium vitis-idaea

Vicia faba

Vigna sinensis (Vigna unguioulata) - Vitis vinifera Zea mays

Olive name millet bean bean bush bean parsley spruce fir pine pea cherry plum almond peach pear currant red gooseberry castor sugar cane rye sesame potatoes sorghum bicolour sorghum spinach cacao clover wheat blueberries cranberries bean grape vine directed

In order to broaden the spectrum of action and to achieve synergistic effects, the new substituted cyclohexenone derivatives can be mixed with one another and with numerous representatives of other herbicidally active or growth-regulating groups of active substances and then applied together.

Examples of suitable compounds for this purpose are: palzines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, derivatives benzofuran, quinolinecarboxylic acids and others.

In addition, it may be useful to apply the new herbicidal compositions alone or in combination with other herbicides also with other plant protection agents, for example with pest control agents or phytopathogenic fungi or bacteria. Miscibility with mineral salt solutions, which are used to eliminate nutrient and trace element deficiencies, is also of importance. Non-phytotoxic oils and oil concentrates may also be added.

Claims (5)

OBJECT OF THE INVENTION A herbicidal composition comprising, as an active ingredient, in addition to inert additives, 0.1 to 95% by weight of at least one cyclohexenone derivative of the formula I OH n ^{1 0} in which A represents a cycloalkyl group having 5 to 12 ring members to which one or two oxirane or thiirane rings is fused and which is optionally substituted by up to four methyl groups and bridged by an alkylene chain of not more than 3 carbon atoms; represents a hydrogen atom, a methoxycarbonyl group or a cyano group, R is C 1 -C 4 alkyl and R is C 1 -C 3 alkyl, C 3 or C 4 alkenyl, C 3 or C 4 haloalkyl, C 1 -C 3 halo substituents or propargyl, or salts thereof. 2. A composition according to claim 1, wherein the active ingredient comprises at least one cyclohexenone derivative of the formula I, wherein: A is a 5- to 8-membered cycloalkyl group to which one or two oxirane or thiirane rings are fused and which is optionally substituted with up to 4 methyl groups and bridged with an alkylene chain of up to 3 carbon atoms, And R, R and R are as defined in 1, or a salt thereof. 3. A composition according to claim 1, wherein the active ingredient comprises at least one cyclohexenone derivative of the formula I wherein R is hydrogen and the other substituents are as defined in claim 1, or a salt thereof. 4. A composition according to claim 1, characterized in that it contains as active ingredient at least one cyclohexenone derivative of the formula I in which R represents alkyl having 2 or 3 carbon atoms and R ^1, A and R ^J are as defined in paragraph 1 or a salt thereof. 5. A process for the preparation of an active ingredient according to claim 1, wherein the compound of formula II (II) is: Rl O in which 1 2 k, R and R have the meaning given in point 1, act a) an ammonium compound of the general formula R ³ O - NH ³ Y in which R is as defined in 1 a Y is an anion, in an inert diluent optionally in the presence of water at a temperature between 0 and 80 ° C of the base or b) a hydroxylamine derivative of the general formula R ³ O-NB ₂ , wherein it is as defined in 1, optionally present in an aqueous solution, in an inert solvent.