HU216276B - Herbicidal compositions containing optically active cyclohexenone oxime ethers, process for producing the activ ingredients and method for combating weeds - Google Patents

Abstract

The present invention is acutely active, in the form of the R-and S-stone configurations of the oxymethyl ether moiety, and at least 75% by weight of cyclohexenone-oxime ether of general formula (I) consisting of the R-stone rendering molds and the prodrug formulations thereof which are agriculturally active as active ingredient (I). ) for the preparation of a cyclohexenone-oxime ether of the general formula for the process of vitrification, and the invention relates to a method for destroying vermin formulations. and R2 represents (1-4C-alkyl alkylthio) - (1-6C-alkyl) -corrosion, in the case of addition of 1-4 carbon atoms, alkylthio-tuberculosyltransferred 3–7-Carbon cyclic tube tube, 5–7-C-Cyclic Cyclic Core, in case 1–3 halogen, Nitrogen, C 1-4 alkylcarbon and / or C 3-6 alkynyloxy-xylophenyltinylphenylphenyl, or, as anhydrous, sulfuric or sulfuric acid, 6-membered saturated heterocyclic tube. ŕ

Description

The present invention relates to optically active herbicidal compositions containing cyclohexenone oxime ethers of formula I and their agriculturally acceptable salts as an active ingredient in the oxime ether portion having the R and S configuration and containing at least 75 mol% of the R configuration. ethers as well as the weed control process with the herbicidal compositions of the present invention.

In formula I, R ¹ is C 1 -C 6 alkyl,

X is halogen or C 1 -C 4 alkyl, n is 1 or 2, and

R ² is (C 1 -C 3 alkylthio) - (C 1 -C 6) alkyl, (C 3 -C 7) cycloalkyl optionally substituted with (C 1 -C 4) alkylthio, (C 5 -C 7) cycloalkenyl, optionally 1 Phenyl substituted with -3 halogen, nitro, C 1-4 alkyl and / or C 3-6 alkyloxy groups, or a 6-membered saturated heterocyclic group containing an oxygen or sulfur atom as a heteroatom.

Herbicides are already known in the art

Cyclohexanedione derivatives of the general formula wherein R ^c , R ^d and R ^{e may have,} inter alia, the following meanings:

- US 4,440,566 (R ^c = ethyl, propyl; R ^d = benzyl; R ^e = 2 (ethylthio) propyl;

EP-A 238 021 and EP-A 125094 (R c = ethyl, propyl; R ^d = benzyl, 2-butenyl; R ^e = substituted 5-membered heteroaryl);

EP-A 80301 (R ^c = ethyl, propyl; R ^d = benzyl, 2-butenyl; R ^e = substituted phenyl);

DE-A 38 38 309 (R ^c = ethyl, propyl; R ^d = substituted 4-phenylbutylene or 4-phenylbutenylene; R ^c = substituted 5-7 membered heterocyclic group);

EP-A 456112 (R ^c = ethyl, propyl; R ^d = substituted 3-phenoxypropylene or 2-phenoxyethylene; R ^e = substituted 5-7 membered heterocyclic group). However, the herbicidal activity of these compounds, in particular their selectivity against non-grass weeds, is only marginally satisfactory.

It was an object of the present invention to provide novel mixtures of cyclohexenone oxime ethers which exhibit improved selectivity for non-woody weeds, such as rice and maize.

It has now been found that mixtures of optically active cyclohexenone oxime ethers of formula I as defined above fulfill this function. In addition, we have found herbicidal compositions containing these mixtures as active ingredients.

Mixtures of optically active cyclohexenone oxime ethers of the formula I can be obtained in various ways, preferably in the manner known per se, from the known cyclohexenone derivatives of the formula II (see DE-A 38 38 309, EP-A 243 313, EP-A 456 112). suitable mixtures of active hydroxylamine derivatives of formula III (see EP-A 169 521).

The reaction is conveniently carried out using a suitable salt of the hydroxylamine derivative of formula ΙΠ, in particular its hydrochloride, and is carried out in a heterogeneous phase in an inert solvent such as dimethylsulfoxide, alcohol such as methanol, ethanol, isopropanol, aromatic hydrocarbon such as benzene. and toluene, chlorinated hydrocarbons such as chloroform, 1,2-dichloroethane, aliphatic hydrocarbons such as hexane and cyclohexane, esters such as ethyl acetate or ether such as diethyl ether, dioxane and tetrahydrofuran.

The reaction is carried out in the presence of a base, and in general 0.5 to 2 molar equivalents of the base, based on the amount of the compound of formula III, is sufficient.

Suitable bases for the reaction include carbonates, bicarbonates, acetates, alcoholates, oxides or hydroxides of alkali metals and alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide, and suitable bases include organic bases such as pyridine and tertiary amines such as triethylamine. Preferably, the reaction is carried out in methanol in the presence of sodium bicarbonate as the base.

A variation of the preparation reaction is that the reaction is carried out without addition of a base with a free hydroxylamine base of formula III, for example an aqueous solution of a hydroxylamine base, and one or two phase depending on the solvent used for the compound of formula II. a reaction mixture is obtained.

Suitable solvents for this variant of the reaction include alcohols such as methanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatic, optionally chlorinated hydrocarbons such as hexane, cyclohexane, methylene dichloride, toluene and 1,2-dichloro. ethane, esters such as ethyl acetate, nitriles such as acetonitrile and cyclic ethers such as dioxane and tetrahydrofuran.

It is desirable to react the cyclohexenone derivatives of formula II and mixtures of optically active hydroxylamine derivatives of formula III in about a stoichiometric ratio;

The reaction temperature is usually 0 ° C to the boiling point of the reaction mixture, but preferably 20 ° C to 80 ° C.

The reaction is completed in a few hours. The product obtained can be isolated from the reaction mixture in a conventional manner, for example by evaporation of the reaction mixture, removal of the residue by dichloromethane / water and evaporation of the solvent in vacuo.

No special pressure conditions are required, generally the reaction is carried out at atmospheric pressure or under the actual diluent pressure.

By virtue of their acidic nature, the optically active cyclohexenone oxime ethers of formula I may form enol esters and salts with alkali metal and alkaline earth metal compounds.

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To prepare the alkali metal salts, the 3-hydroxycyclohexenone derivative is treated with sodium or potassium hydroxide or alcoholate in aqueous solution or in organic solvents such as methanol, ethanol, acetone and toluene.

Other metal salts, such as manganese, copper, zinc, iron, calcium, magnesium and barium salts, may be prepared from the sodium salts in the usual manner, as well as ammonium, phosphonium, sulfonium and sulfoxonium salts with ammonium, phosphonium and sulfoxonium hydroxides.

Esters of the compounds of formula I can also be obtained in conventional manner (see, for example, Organicum, VEB Deutscher Verlag dér Wissenschaften, 17th edition, Berlin, 1988, pages 405-408).

The novel mixtures of optically active hydroxylamine derivatives of formula III can be prepared from known compounds through a number of known reaction steps, as shown in Scheme A. In formula V, L is a eliminating group, such as halogen, such as chlorine, bromine and iodine, or methylsulfonyloxy.

Preferably, the optically active alkylating agent of formula V is described in Tetrahedron Letters, 29, 5493 (1988);

J. Org. Chem., 52, 3587 (1987); EP-A 172 719; EP-A 230379; U.S. Pat. No. 4,841,079, or, if desired, the optically active methanol derivative of formula IV [Chem. Pharm. Bull., 33, 1955 (1985)] may be reacted according to the method of Mitsunobu [Synthesis, 1, 1981; J. Med. Chem., 33, 187 (1990)] with the cyclized hydroxyimide of formula VI and the resulting protected hydroxylamine of formula VII, for example 2-aminoethanol. free, optically active hydroxylamine derivative.

In formula VI, D may be, for example, a divalent group consisting of ethylene, trimethylene, vinylene or a 5 or 6 membered saturated, partially unsaturated or aromatic ring compound containing a nitrogen atom, such as phenylene, pyridinidyl, cyclopentylene, cyclohexylene. - or cyclohexenylene.

Examples of cyclic hydroxyimide derivatives of formula VI include N-hydroxyphthalimide, N-hydroxy-maleimide, N-hydroxy-quinolinimide, N-hydroxy-1,2-cyclohex-1-ene-dicarboximide, N -hydroxysuccinimide, N-hydroxy-1,2-cyclohex-4-ene dicarboximide, N-hydroxyglutarimide.

The reaction of the optically active alkylation beads of formula V with a cyclic hydroxyimide derivative of formula VI is conveniently carried out in the presence of a base. In principle, any base capable of deprotonating the hydroxyimide of formula VI without destroying its imide structure is suitable for this purpose. Such bases are mainly so-called non-nucleophilic bases.

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

The following bases are listed individually, as examples: sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, bicarbonates of these metals, trimethylamine, triethylamine, tributylamine, ethyl diisopropylamine, N, N-dimethylaniline, 4- (dimethylamino) pyridine, diazabicyclooctane, diazabicycloundecane, N-methylpiperidine, 1,4-dimethylpiperazine, pyridine, quinoline, bipiridil, phenanthroline. Sodium and potassium carbonate are preferred bases because of their low cost.

The base is generally added in an amount ranging from one equivalent to an excess of 5 equivalents relative to the hydroxyimide derivative. A larger excess can be used, but this generally has no further advantages. Similarly, a smaller amount of the base may be used in the reaction. Preferably, however, 1-3, especially 1-2 equivalents, of base are added to the reaction mixture, based on the hydroxyimide derivative VI.

Nucleophilic bases, such as alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, are also possible in the reaction. However, in this case, it is preferable to apply the base in an equivalent amount to the hydroxyimide derivative of formula VI to avoid nucleophilic attack of the hydroxide ion on the carbonyl portion of the imide group.

The optically active alkylating agent of formula V and the hydroxyimide derivative of formula VI are conveniently reacted in a solvent which remains inert under the reaction conditions. Preferred solvents for this purpose include polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, and cyclic ethers. The amount of solvent is generally not critical.

The reaction of the optically active alkylating agents of formula V with the hydroxyimide derivatives of formula VI may also be carried out using phase transfer catalysis. In this case, solvents which form a biphasic mixture with water, preferably chlorinated hydrocarbons, are used.

Phase transfer catalysts suitable for the reaction include quaternary ammonium and phosphonium salts, polyethylene glycols, polyethylene glycol ethers and crown ethers commonly used for this purpose, such as those described in Dehmlow et al., Phase Transfer Catalysis, 37 . pages 86-93. Verlag Chemie, Weinheim, 1980.

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

The reaction of the optically active alkylation beads of formula V with the hydroxyimide derivative of formula VI generally takes place at a temperature of 0 ° C to 140 ° C, preferably 2 ° C to 100 ° C, especially 40 ° C to 80 ° C. It is preferable to carry out the reaction by adding the alkylating agent V to the solvent mixture of the hydroxyimide VI and the base. It may be advantageous if the hydroxyimide derivative has a lower temperature

The reaction mixture is added to the reaction mixture at a temperature of, for example, 0 ° C to 50 ° C, and the temperature of the reaction mixture is then raised to the actual reaction temperature.

After completion of the reaction, water is conveniently added to the cooled reaction mixture to form the resulting hydroxylamine derivative VII as a crystalline solid or oil. The hydroxylamine derivative thus obtained may, if desired, be further purified by recrystallization or extraction.

The hydroxylamine derivatives of formula VII thus obtained can be stored or converted into the optically active hydroxylamine derivatives of formula III which have a free amino group immediately.

This conversion reaction can be carried out by methods known per se, such as those described in DE-A 36 15 973 and references cited therein. It is preferred to use the process according to DE-A 3615 973 wherein the optically active hydroxylamine derivative of formula III is liberated with ethanolamine. The optically active hydroxylamine derivatives of formula III may also be liberated by other bases such as aqueous mineral bases, amines, hydrazines, hydroxylamines or even aqueous acids.

The optically active hydroxylamine derivatives of the general formula (III) can be isolated from the reaction mixtures obtained by these processes by conventional methods such as crystallization or extraction. In order to increase the tendency to crystallize hydroxylamine derivatives of formula III, it may often be advantageous to convert these compounds to their salts with mineral acids or organic acids. For this purpose, a dilute solution of these acids is generally reacted with an equivalent amount of a hydroxylamine derivative. The resulting hydroxylammonium salts, such as the optically active hydroxylamine derivatives of formula III containing the free amino group, can be directly converted to the optically active corresponding cyclohexenone oxime ethers of formula I or stored as desired.

The optical purity of intermediates of Formula III and cyclohexenone oxime ethers of Formula I is dependent upon the optical purity of the methanol derivative of formula IV used and the alkylation agent of formula V. In the process of the invention, the reaction is carried out using a methanol derivative of formula IV or an alkylating agent of formula V having the highest possible optical isomer purity, always producing an isomeric mixture of optically active hydroxylamine derivatives of formula III and cyclohexenone oximeters of formula I in the substituted carbon atom (in the oxime ether moiety) the ratio of the R-configuration isomer is at least 75, but in particular 90-100 mol%.

The optically active cyclohexenone oxime ethers of formula I can be prepared as isomeric mixtures in which both the E / Z isomeric mixtures (relative position of the oxime ether moiety relative to R ¹ ) and the diastereomeric mixtures are possible. These isomeric mixtures may, if desired, be separated into their components by customary methods such as chromatography or crystallization.

The optically active cyclohexenone oxime ethers of formula I can be depicted in several tautomeric forms.

Preferred herbicidal compounds are those compounds of formula I wherein R ¹ is C 1-6 alkyl such as methyl, ethyl, propyl, butyl, pentyl or hexyl and their branched isomers, especially ethyl or propyl. ;

X is halogen, especially fluorine, chlorine or bromine, or C 1 -C 4 alkyl, especially methyl, most preferably halogen; for n 2, X may be different or have the same meaning;

Where ^R2 is an alkylthio group, especially methylthio or ethylthio group is 1-, 2- or 3-position may be, in particular preferably 2- (ethylthio) propyl; C 3-7 -cycloalkyl and C 5-7 -cycloalkenyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclopentenyl, cyclohexenyl or cyclohexenyl; alkylthio-substituted cycloalkyl is especially 1- (methylthio) cyclopropyl; a 6-membered saturated heterocyclic group such as tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl or dioxepan-5-yl; the substituents on the phenyl group may be the same or different.

Salts of the compounds of the formula I are agriculturally acceptable salts such as alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as calcium, magnesium and barium salts, and manganese, copper, zinc or iron salts, and ammonium, phosphonium, or sulfoxonium salts, preferably tetraalkylammonium, benzyltrialkylammonium, trialkylsulfonium and trialkylsulfoxonium salts. Synthesis Example:

Example for the preparation of compounds of formula I:

Example 1 (R) -2- {1- [2- (4-Chloro-phenoxy) -propyloxyimino] -propyl} -3-hydroxy-5- [1- (methylthio) cyclopropyl] cyclohex-2-ene-l-one

1.0 g (3.9 mmol) of 3-hydroxy-5- [1- (methylthio) -cyclopropyl] -2-propionyl-cyclohex-2-en-1-one, 0.95 g (4.7) A mixture of (R) - (2- (4-chlorophenoxy) propoxy) amine (80 mmol) in methanol (80 mL) was stirred for 24 hours and the reaction mixture was concentrated in vacuo. The residue is taken up in methyl tert-butyl ether and the ether phase is extracted with 10% (w / w) aqueous sodium hydroxide. The aqueous phase is extracted with methyl tert-butyl ether and then acidified with 10% hydrochloric acid. Finally, the aqueous solution was extracted once more with methyl tert-butyl ether. The organic layer was dried over sodium sulfate and concentrated in vacuo to afford the title compound. Yield: 59%

Specific optical rotation:

[α] ²⁰ D = -13.1 (c = 1.0 in methanol)

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

Example of Preparation of Starting Compounds:

Example 2 (R) - [2- (4-Chlorophenoxy) propoxyamine]

23.3 g (0.143 mol) of N-hydroxyphthalimide, 33.3 g (0.127 mol) of triphenylphosphine and 23.7 g (0.127 mol) of (R) -2- (4-chlorophenoxy) propanol [ CAS reg. number: 92471-63-1; Chem. Pharm. Bull, 33, 1955 (1985)] was slowly added dropwise azodicarboxylic acid diethyl ester (24.9 g, 0.143 mol). After the slightly exothermic reaction was complete, the reaction mixture was stirred for an additional órán15 hours and then concentrated. The residue was chromatographed on silica gel (cyclohexane / ethyl acetate = 1: 1) to give (R) N- (2- (4-chlorophenoxy) propoxy) phthalimide (42 g).

To the crude phthalimide crude product thus obtained is slowly added 100 ml of ethanolamine. The reaction mixture was stirred at 60 ° C for 5 hours, then poured into ice water and extracted with dichloromethane. The combined organic layers were washed with water, dried over sodium sulfate and evaporated in vacuo to give the title compound. Yield: 81%

Specific optical rotation:

[a] ² D ^s = -20.8 (c = 1.0, methanol) ¹H-NMR spectrum (360 MHz, CDC1 _3): δ = 1.25 ppm (d, 3H); 3.75 ppm (dd, 1H); 3.85 ppm (dd, 1H);

4.65 ppm (m, 1H); 5.50 ppm (bs, 2H); 6.90 ppm (d,

2 H); 7.20 ppm (d, 2H).

Table 1 below lists further optically active hydroxylamine derivatives of Formula III which were prepared or prepared in the same manner.

2-8. Table I contains the optically active cyclohexenone oxime ethers of formula I according to the invention.

Table 1

Compounds of formula III

Song Specific optical rotation [α] β (c = 1.0, in methanol) 1:01 2-C1 -34.1 1:02 3-C1 -23.2 1:03 4-C1 -20.8 1:04 2,4-Cl ₂ -27.5 1:05 2-CH3, 4-C1 -26.2 1:06 2,4-F ₂ -21.5 1:07 4-F -27.5

Table 2

Compounds of formula I wherein X 1 = 2-Cl

Song R ¹ R ² Specific optical rotation [a] p ( ^{c =} 1>9> in methanol) 2:01 ethyl (RS) -2-tetrahydropyran-3-yl -42.0 2:02 ethyl (R) -2-tetrahydropyran-3-yl 2:03 ethyl (S) -2H-tetrahydropyran-3-yl 2:04 ethyl 2H-tetrahydropyran-4-yl -37.2 2:05 ethyl (RS) -2H-tetrahydrothiopyran-3-yl -34.6 2:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 2:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 2:08 propyl (RS) -2-tetrahydropyran-3-yl -33.6 2:09 propyl (R) -2H-tetrahydropyran-3-yl 2:10 propyl (S) -2H-tetrahydropyran-3-yl 2:11 propyl 2H-tetrahydropyran-4-yl -38.9 2:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -27.6 2:13 propyl (R) -2H-Tetrahydrothiopyran-3-yl 2:14 propyl (S) -2-tetrahydrothiopyran-3-yl 2:15 ethyl phenyl 2:16 ethyl 2,4,6-trimethylphenyl 2:17 ethyl 4- (2-propynyloxy) phenyl 2:18 propyl 4-fluoro-3-nitrophenyl 2:19 propyl (RS) -2- (ethylthio) propyl 2:20 ethyl 1- (methylthio) cyclopropyl 2:23 propyl (RS) cyclohex-3-enyl

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Table 3

Compounds of formula I wherein Χ „= 3-Ο

Song R ¹ R ² Specific optical rotation [aj ² ; (c = 1.0, in methanol) 3:01 ethyl (RS) -2-tetrahydropyran-3-yl -13.2 3:02 ethyl (R) -2-tetrahydropyran-3-yl 3:03 ethyl (S) -2H-tetrahydropyran-3-yl 3:04 ethyl 2H-tetrahydropyran-4-yl -17.1 3:05 ethyl (RS) -2-tetrahydrothiopyran-3-yl -11.8 3:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 3:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 3:08 propyl (RS) -2-tetrahydropyran-3-yl -11.7 3:09 propyl (R) -2-tetrahydropyran-3-yl 3:10 propyl (S) -2H-tetrahydropyran-3-yl 3:11 propyl 2H-tetrahydropyran-4-yl -12.5 3:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -8.3 3:13 propyl (R) -2H-Tetrahydrothiopyran-3-yl 3:14 propyl (S) -2-tetrahydrothiopyran-3-yl 3:15 ethyl phenyl 3:16 ethyl 2,4,6-trimethylphenyl -15.6 3:17 ethyl 4- (2-propynyloxy) phenyl -14.9 3:18 propyl 4-fluoro-3-nitrophenyl -11.9 3:19 propyl (RS) -2- (ethylthio) propyl -12.7 3:20 ethyl 1- (methylthio) cyclopropyl -14.9 3:23 propyl (RS) cyclohex-3-enyl 15.0 3:24 propyl 1- (methylthio) cyclopropyl -15.1

Table 4

Compounds of formula I wherein X 1 = 4-Cl

Song R ¹ R ² Specific optical rotation [α] j (c = 1.0, in methanol) 4:01 ethyl (RS) -2H-tetrahydropyran-3-yl 1 -11.9 4:02 ethyl (R) -2-tetrahydropyran-3-yl 4:03 ethyl (S) -2H-tetrahydropyran-3-yl 4:04 ethyl 2H-tetrahydropyran-4-yl -12.4 4:05 ethyl (RS) -2-tetrahydrothiopyran-3-yl -10.3 4:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 4:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 4:08 propyl (RS) -2-tetrahydropyran-3-yl -10.8 4:09 propyl (R) -2-tetrahydropyran-3-yl 4:10 propyl (S) -2H-tetrahydropyran-3-yl 4:11 propyl 2H-tetrahydropyran-4-yl -8.9 4:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -12.1 4:13 propyl (R) -2-tetrahydrothiopyran-3-yl 4:14 propyl (S) -2-tetrahydrothiopyran-3-yl 4:15 ethyl phenyl -12.6

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Table 4 (continued)

Song R> R ² Specific optical rotation [α] j (c = 1.0, in methanol) 4:16 ethyl 2,4,6-trimethylphenyl -13.0 4:17 ethyl 4- (2-propynyloxy) phenyl -13.0 4:18 propyl 4-fluoro-3-nitrophenyl -8.1 4:19 propyl (RS) -2- (ethylthio) propyl -11.5 4:20 ethyl 1- (methylthio) cyclopropyl -13.1 4:23 propyl (RS) -cyclohex-3-enyl 4:24 propyl 1- (ethylthio) cyclopropyl -9.7 4:25 ethyl 1- (ethylthio) cyclopropyl -12.3 4:26 propyl 1- (propylthio) cyclopropyl -9.1 4:27 ethyl 1- (propylthio) cyclopropyl -12.6

Table 5

Compounds of formula I wherein X _n = 2,4-Cl ₂

Song R ¹ R ² Specific optical rotation [a] j (c = 1.0, in methanol) 5:01 ethyl (RS) -2-tetrahydropyran-3-yl -36.5 5:02 ethyl (R) -2-tetrahydropyran-3-yl 5:03 ethyl (S) -2H-tetrahydropyran-3-yl 5:04 ethyl 2H-tetrahydropyran-4-yl -35.5 5:05 ethyl (RS) -2-tetrahydrothiopyran-3-yl -25.3 5:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 5:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 5:08 propyl (RS) -2-tetrahydropyran-3-yl -32.5 5:09 propyl (R) -2-tetrahydropyran-3-yl 5:10 propyl (S) -2H-tetrahydropyran-3-yl 5:11 propyl 2H-tetrahydropyran-4-yl -34.2 5:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -22.2 5:13 propyl (R) -2-tetrahydrothiopyran-3-yl 5:14 propyl (S) -2-tetrahydrothiopyran-3-yl 5:15 ethyl phenyl 5:16 ethyl 2,4,6-trimethylphenyl 5:17 ethyl 4- (2-propynyloxy) phenyl 5:18 propyl 4-fluoro-3-nitrophenyl 5:19 propyl (RS) -2- (ethylthio) propyl 5:20 ethyl 1- (methylthio) cyclopropyl 5:23 propyl (RS) cyclohex-3-enyl

Table 6

Compounds of formula I wherein X _n = 2-CH ₃ , 4-Cl

Song R ¹ R ² Specific optical rotation [α] o (c = 1.0, in methanol) 6:01 ethyl (RS) -2-tetrahydropyran-3-yl -26.5 6:02 ethyl (R) -2-tetrahydropyran-3-yl

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Table 6 (continued)

Song R ¹ R ² Specific optical rotation [a] (j) (c = 1.0, in methanol) 6:03 ethyl (S) -2H-tetrahydropyran-3-yl 6:04 ethyl 2H-tetrahydropyran-4-yl -16.3 6:05 ethyl (RS) -2-tetrahydrothiopyran-3-yl -17.1 6:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 6:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 6:08 propyl (RS) -2-tetrahydropyran-3-yl -24.7 6:09 propyl (R) -2-tetrahydropyran-3-yl 6:10 propyl (S) -2H-tetrahydropyran-3-yl 6:11 propyl 2H-tetrahydropyran-4-yl -24.9 6:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -19.0 6:13 propyl (R) -2-tetrahydrothiopyran-3-yl 6:14 propyl (S) -2-tetrahydrothiopyran-3-yl 6:15 ethyl phenyl 6:16 ethyl 2,4,6-trimethylphenyl 6:17 ethyl 4- (2-propynyloxy) phenyl 6:18 propyl 4-fluoro-3-nitrophenyl 6:19 propyl (RS) -2- (ethylthio) propyl 6:20 ethyl 1- (methylthio) cyclopropyl 6:21 ethyl 1,3-dimethyl-5-pyrazolyl 6:22 propyl 3-isopropyl-5-isoxazolyl 6:23 propyl (RS) -cyclohex-3-enyl

Table 7

Compounds of formula I wherein X _n = 2,4-F ₂

Song R ¹ R ² Specific optical rotation [a] j (c = 1.0, in methanol) 7:01 ethyl (RS) -2H-tetrahydropyran-3-yl -9.2 7:02 ethyl (R) -2-tetrahydropyran-3-yl 7:03 ethyl (S) -2H-tetrahydropyran-3-yl 7:04 ethyl 2H-tetrahydropyran-4-yl -13.2 7:05 ethyl (RS) -2H-tetrahydrothiopyran-3-yl -10.5 7:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 7:07 ethyl (S) -2H-tetrahydrothiopyran-3-yl 7:08 propyl (RS) -2-tetrahydropyran-3-yl -6.6 7:09 propyl (R) -2-tetrahydropyran-3-yl 7:10 propyl (S) -2H-tetrahydropyran-3-yl 7:11 propyl 2H-tetrahydropyran-4-yl -15.3 7:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -13.8 7:13 propyl (R) -2-tetrahydrothiopyran-3-yl 7:14 propyl (S) -2-tetrahydrothiopyran-3-yl 7:15 ethyl phenyl -15.3 7:16 ethyl 2,4,6-trimethylphenyl -17.3 7:17 ethyl 4- (2-propynyloxy) phenyl -14.7

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Table 7 (continued)

Song R * R ² Specific optical rotation [α] ² j (c = 1.0, in methanol) 7:18 propyl 4-fluoro-3-nitrophenyl H, 3 7:19 propyl (RS) -2- (ethylthio) propyl -10.5 7:20 ethyl 1- (methylthio) cyclopropyl -14.6 7:23 propyl (RS) -cyclohex-3-enyl -13.4 7:24 propyl 1- (methylthio) cyclopropyl -8.9

Table 8

Compounds of formula I wherein X _n = 4-F

Song R ¹ R ² Specific optical rotation [α] ² (c = 1.0, in methanol) 8:01 ethyl (RS) -2-tetrahydropyran-3-yl -19.2 8:02 ethyl (R) -2-tetrahydropyran-3-yl 8:03 ethyl (S) -2H-tetrahydropyran-3-yl 8:04 ethyl 2H-tetrahydropyran-4-yl -19.1 8:05 ethyl (RS) -2-tetrahydrothiopyran-3-yl -17.9 8:06 ethyl (R) -2-tetrahydrothiopyran-3-yl 8:07 ethyl (S) -2-tetrahydrothiopyran-3-yl 8:08 propyl (RS) -2-tetrahydropyran-3-yl -18.3 8:09 propyl (R) -2-tetrahydropyran-3-yl 8:10 propyl (S) -2H-tetrahydropyran-3-yl 8:11 propyl 2H-tetrahydropyran-4-yl -21.9 8:12 propyl (RS) -2-tetrahydrothiopyran-3-yl -17.9 8:13 propyl (R) -2-tetrahydrothiopyran-3-yl 8:14 propyl (S) -2-tetrahydrothiopyran-3-yl 8:15 ethyl phenyl -18.3 8:16 ethyl 2,4,6-trimethylphenyl -19.3 8:17 ethyl 4- (2-propynyloxy) phenyl -20.3 8:18 propyl 4-fluoro-3-nitrophenyl -16.5 8:19 propyl (RS) -2- (ethylthio) propyl -14.5 8:20 ethyl 1- (methylthio) cyclopropyl -19.1 8:23 propyl (RS) cyclohex-3-enyl -20.5 8:24 propyl 1- (methylthio) cyclopropyl -18.4

The optically active cyclohexenone oxime ethers of formula I can be used both as isomeric mixtures and as pure isomers as active ingredients in herbicides, especially for controlling weeds of the Gramineae family (grasses). In general, they are well tolerated by broadleaf crop plants as well as monocotyledonous non-Gramineae crops, so that these compounds act selectively among the above crop plants. Some of the cyclohexenone oxime ethers of formula I according to the invention are also suitable for selective control of weeds among crop plants belonging to the Gramineae family.

The optically active cyclohexenone50 oxime ethers of Formula I, or herbicidal compositions containing them as active ingredients, may be used, for example, in the form of directly sprayable solutions, powders, suspensions, aqueous, oily or other suspensions or dispersions, emulsions, oily dispersions, in the form of sprays or granules by spraying, smoking, dusting, spraying or sprinkling. The application forms are adapted to the purpose of use; in all cases, the formulations should be such as to distribute the active ingredients of the invention as evenly as possible.

HU 216 276 Β

The compounds of formula I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions. Medium to high-boiling mineral oil fractions, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, , alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone or highly polar solvents such as N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone or water.

Aqueous formulations may be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water dispersible granules by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the active compounds, either alone or in an oil or solvent, may be homogenized in water with the aid of wetting, tackifying, dispersing or emulsifying agents. Water-dilutable concentrates may also be prepared consisting of the active ingredient, a wetting agent, a tackifier, a dispersant or emulsifier, and optionally a solvent or oil.

Surfactants may include aromatic sulfonic acids such as lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acids, as well as fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohols. alkali metal, alkaline earth metal and ammonium salts of sulphates and salts of sulphated hexa-, hepta- and octadecanols and glycol ethers of fatty alcohols; (oxyethylene) octylphenyl ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl and tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols with ethylene oxide, ethoxylated castor oil, polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol pol iglycol ether acetate, sorbitol ester, lignin sulphite waste liquors or methylcellulose.

Powders, spreads and dusts may be prepared by mixing or grinding the active ingredient with a solid carrier.

Granules, such as coated, impregnated and homogeneous granules, may be prepared by binding the active ingredient to solid carriers. Mineral products such as silicas, silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground magnesium oxide may be used as solid carriers for this purpose. plastics, fertilizers such as ammonium sulfate, phosphate and nitrate, urea and plant products such as cereal flour, cinnamon, wood and bone shells, cellulose powder or other solid carriers.

The compositions contain from 0.01 to 99% by weight of the active ingredient, usually from 0.1 to 95%, preferably from 0.5 to 90% by weight. In formulations, the active compounds are generally 90-100%, but preferably 95-100% pure (based on their NMR spectrum).

Examples of herbicides:

Example 3 A solution consisting of 2.0 parts by weight of active ingredient 2.05 and 10 parts by weight of N-methyl-α-pyrrolidone, which can be applied to the finest droplets.

Example 4: 10 parts by weight of the active ingredient 2.12, 80 parts by weight of xylene, 8 parts by weight of 10 parts by weight of the reaction product of ethylene oxide and 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 40 parts by weight A mixture of the product of the reaction mixture is finely divided in 100,000 parts by weight of water to give an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 5 A mixture of 4.20 parts by weight of active ingredient, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol and 20 parts by weight of the reaction product of 40 mol of ethylene oxide and 1 mol of castor oil, finely divided in 100,000 parts by water.

Example 6 A mixture of 4 parts by weight of active ingredient 4.12, 25 parts by weight of cyclohexanone, 65 parts by weight of petroleum fractions having a boiling range of 210-280 ° C and 10 parts by weight of reaction product of 40 moles of ethylene oxide and 1 mole of castor oil. an aqueous dispersion is obtained.

Example 7 A mixture of the active ingredient 4.19, 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 10 parts by weight of lignin sulfonic acid sodium salt from sulfite slurry and 7 parts by weight of powdered silica gel in a hammer mill, milled in 20 milliliters 0.1% by weight of active ingredient is obtained.

EXAMPLE 8 A mixture of part by weight of active ingredient 6.01 and 97 parts by weight of finely divided kaolin, which is a powder containing 3% by weight of active ingredient.

Example 9 A mixture of 8 parts by weight of active ingredient 6.05 and 92 parts by weight of paraffin oil sprayed onto 92 parts by weight of powdered silica gel which gives the active ingredient a good adhesion.

Example 10 10 parts by weight of active ingredient 6.11, 10 parts by weight (phenolsulfonic acid / urea / formaldehyde condens

A stable aqueous dispersion of sodium salt, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted with water.

EXAMPLE 11 2 parts by weight of active ingredient 6.12, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of fatty alcohol, 20 parts by weight of sodium salt of phenolsulfonic acid / urea / formaldehyde condensate and 68 parts of paraffinic oil.

EXAMPLE 12 Compound of active ingredient 2.01, 4 parts of diisobutylnaphthalene-α-sulfonic acid sodium salt, 20 parts of lignin sulfonic acid sodium salt from sulphite slurry, 38 parts of silica gel and 38 parts of kaolin in 100 parts hammer mill, finely divided to form a 0.1% w / w spray.

The use of herbicides or active ingredients may occur before or after emergence. If certain crop plants have low tolerance to the active ingredients, then a spraying technique can be used, whereby the herbicidal composition is applied by spraying so that the leaves of the sensitive crop are not touched at all while the active compounds are applied to undergrowth -directed, lay-by).

The amount of active ingredient used is from 0.001 to 3, preferably from 0.01 to 1 kg of active ingredient / ha, depending on the purpose of the weed control, the season, the species of weed to be controlled and the stage of growth.

In view of the wide variety of uses, the compounds of the present invention and compositions containing them as active ingredients can be used to control weeds on a large number of crop plants. Examples of such crops include:

Allium cepa (onion), Ananas comosus (pineapple), Arachis hypogaea (peanuts), Asparagus officinalis (asparagus), Beta vulgaris spp. altissima (sugar beet), Beta vulgaris spp. rapa (fodder beet), Brassica napus var. napus (cabbage rape), Brassica napus var. napobrassica (turnip), Brassica rapa var. silvestris (beet), Camellia sinensis (tea bush), Carthamus tinctorius (garden safflower), Carya illinoinensis (chicory), Citrus limon (lemon), Citrus sinensis (orange), Coffea arabica, -canephora, -liberica (coffee) (cucumber), Cynodon dactylon (bermuda grass), Daucus carota (carrot), Elaeis guineensis (oil palm), Fragaria vesca (strawberry), Glycine max (soybean), Gossypium hirsutum, -arboreum, -herbotum, -vitafol annuus (sunflower), Hevea brasiliensis (rubber), Hordeum vulgare (barley), Humulus lupulus (hops), Ipomoea batatas (sweet potato), Juglans regia (walnut), Lens culinaris (lentil), Linum usitatissimum (rosters) tomato), Malus spp. (apple), Manihot esculenta (manioc), Medicago sativa (alfalfa), Musa spp. (banana), Nicotiana tabacum, -rustica (tobacco), Olea europaea (olive tree), Oryza sativa (rice), Phaseolus lunatus, -vulgar (bean), Picea abies (spruce), Pinus spp. (pine), Pisum sativum (pea), Prunus avium (cherry), Prunus persica (peach), Purus communis (pear), Ribes sylvestre (red currant), Ricinus communis (ricinus), Saccharum officinarum (sugarcane), Secale cereale ( rye), Solanum Tuberosum (potato), Sorghum bicolor, -vulgare (sorghum), Theobroma cacao (cocoa tree), Trifolium pratense (red clover), Triticum aestivum, -durum (wheat), Vicia faba (broad bean), Vitis vinifera , Zea mays (corn).

In order to broaden the spectrum of action and to achieve an increase in efficacy, the optically active cyclohexenone oxime ethers of formula I may be mixed with and co-administered with a number of other herbicides or plant growth regulators.

Examples of the mixture partner include diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroaniline derivatives, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, urea derivatives, diphenyl ether. derivatives, triazinones, uracil derivatives, benzofuran derivatives, cyclohexane-1,3-dione derivatives substituted at the 2-position by, for example, carboxy or carbimino groups, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, heteroaryloxy-phenoxy-propionic acids, their salts, esters and amides, as well as other active ingredients.

In addition, it may be useful to administer the compounds of the formula I, either alone or in combination with other herbicidal agents, in admixture with many other pesticides, such as pests or phytopathogenic fungi or bacteria. It is also important to mix with mineral saline solutions, which can be used to combat nutrient and trace element deficiencies. Non-phytotoxic oils or oil concentrates may also be added.

Examples of impact:

The herbicidal activity of the compounds of formula I is demonstrated in the following greenhouse experiments:

The experimental plants were grown in plastic flower pots containing 3% humus clay sand as substrate. Seeds of experimental plants were sown shallowly by species.

In the case of pre-emergence application, the active ingredients suspended or emulsified in water were dispensed immediately after sowing with a fine spraying device. The experimental culture vessels were lightly watered to allow germination and plant development, and then covered with a transparent plastic bulb until the plants had developed. This coverage ensured uniform germination of the experimental plants, provided that the active ingredients did not influence this.

In the case of post-emergence treatments, experimental plants have already developed in experimental breeding pots or a few days before treatment in experimental cultures11.

They were transplanted into pots. The active ingredients, suspended or emulsified in water, were applied only after reaching a height of 3 to 15 cm, depending on the type of plant. In the case of post-emergence application, the application rates were 0.06 and 0.03 kg active ingredient / ha.

The plants were grown at 10-25 and 20-35 ° C, respectively. The duration of the experiment was 2-4 weeks. During this time, the plants were cared for and their reactions to the treatments evaluated.

The evaluation was done on a scale of 0-100. Here, 100 means that the plants have not emerged at all, or that at least parts of the plant have been completely destroyed, and 0 means that the plants have not been damaged at all or that they have been perfectly normal.

The results of the post-emergence studies with the active compounds 4.12 and 4.20 are described below. The percentage of damage to plants is given.

Experimental plants Active ingredient 4.12 (0.03 kg / ha) 4.20 active ingredient (0.06 kg / ha) Oryza sativa (rice) 20 20 Echinochloa crus-galli 95 100 Setaria viridis 60 100 Setaria italica 95 100

PATENT CLAIMS

Claims (4)

CLAIMS 1. An herbicidal composition comprising as active ingredient 0.01 to 99% by weight of an optically active compound of formula (I) consisting of the isomers of R and S in the oxime ether and at least 75 mol% of the isomer in R cyclohexenone oxime ether or an agriculturally acceptable salt thereof R ¹ is C 1-6 alkyl, X is halogen or C 1 -C 4 alkyl, n is 1 or 2, and R ² is (C 1 -C 4 alkylthio) - (C 1 -C 6 alkyl) thio, C 3 -C 7 cycloalkyl optionally substituted with C 1 -C 4 alkylthio, C 5 -C 7 cycloalkenyl, optionally 1- Phenyl substituted with 3 halogens, nitro, C 1-4 alkyl and / or C 3-6 alkynyloxy, or a 6 membered saturated heterocyclic group containing an oxygen or sulfur atom as a heteroatom contains the usual carrier, diluent and / or with excipients. The herbicidal composition according to claim 1, characterized in that it contains as active ingredient a cyclohexenone oxime ether of formula (R). A process for the preparation of optically active mixtures of a cyclohexenone oximeter of formula (I) as defined in claim 1, R ² , X and n and its agriculturally acceptable salts, characterized in that a cyclohexenone derivative of formula (II) - wherein R ¹ and R ^{2 are} as defined above in an inert organic solvent, in a conventional manner, by reaction with an optically active mixture of a hydroxylamine derivative of formula III, wherein X and na are as defined above. 4. A method of controlling weeds, wherein the weeds or their habitat is treated with at least 0.001 kg / ha of an herbicidal composition in an amount corresponding to the general active ingredient (I) or its agriculturally acceptable salt as defined in claim 1.