HU191024B - Herbicide compositions containing diphenyl-ether derivatives as active substances and process for preparing the active substances - Google Patents

Abstract

The present invention relates to herbicidal compositions which contain as active ingredient substituted diphenyl ethers or a mixture of diphenyl ethers of the general formula in addition to at least one agriculturally permissible additive. The invention provides herbicidally highly effective means for selective weed control.

Description

- C 1 -C 3 alkylene optionally monosubstituted with C 14 alkyl, oxoalkyl or hydroxyalkyl, and

- R ¹ is hydrogen, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, agriculturally acceptable ion, or halogen, C 1 -C 10 alkyl or alkoxy, cyano, nitro or trifluoromethyl optionally mono-, di or trisubstituted phenyl.

The process according to the invention is characterized in that the benzoyl halide of formula II is reacted with an alpha-hydroxycarboxylic acid ester of formula III, A, X, Y, Z, R and R ^{1 are} as defined above, the groups M and Q one is halogen and the other is hydroxy.

FIELD OF THE INVENTION The present invention relates to herbicides containing diphenyl ether derivatives and processes for their preparation.

The diphenyl ether derivatives of the general formula (1):

- represents a nitro group, a halogen atom or a cyano group,

- X represents a hydrogen or halogen atom, - Y represents a hydrogen or halogen atom or a cyano, trifluoromethyl or C 1-4 alkyl group,

-Z represents oxygen or sulfur, -R 1-4 alkyl optionally monosubstituted with C 1-4 alkyl, oxoalkyl or hydroxyalkyl, and - R * represents hydrogen, C 1-10 alkyl, C 3-8 a cycloalkyl group, an agriculturally acceptable ion or a group containing it, or a phenyl group optionally mono-, di- or tri-substituted with a C 1 -C 10 alkyl or alkoxy, cyano, nitro or trifluoromethyl group.

The halogen atoms in the above formula are, for example, bromine, chlorine, iodine or fluorine, preferably bromine or chlorine. Alkylcycloalkyl groups include methyl, ethyl, isobutyl, η-butyl, tert-butyl, η-amyl, heptyl, octyl, isooctyl, monyl, decyl, cyclopropyl, cyclopentyl. , cyclohexyl, cyclooctyl and the like. Suitable alkoxy, oxoalkyl and hydroxyalkyl groups include methoxy, ethoxy, butoxy, octoxy, οχο-ethyl, oxopropyl-χο-butyl, hydroxymethyl, hydroxyethyl, hydroxy. -propylhydroxybutyl and the like. Suitable alkylene groups include, for example, methylene, ethylene or propylene. Examples of agriculturally acceptable ions include alkali metals such as sodium, potassium or lithium, alkaline earth metals such as barium or calcium, ammonium ions or C 1-4 alkylammonium or alkanolammonium.

Compositions of the present invention, preferred are compounds having formula (I) wherein Z is an oxygen atom, a nitro group, R ¹ to 4 carbon atoms, X is hydrogen and Y is halogen.

The compositions of the present invention show excellent herbicidal activity. Particularly preferred are formulations containing, for example, the following compounds as active ingredient: 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; Γ (ethoxycarbonylmethyl) ethyl 5- (2-chloro-4-trifluoromethyl / phenoxy) -2-nitrobenzoate; 2 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethyl) -phenoxy) -2-nitrobenzoate; 1 '(ethoxycarbonyl) -ethyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate; Α-ethoxycarbonyl-2-oxoporyl-5-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) butyl-5- (2-chloro-4- / trifluoromethyl / phenoxy) -2-nitrobenzoate; 1 '- (phenoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate; Γ (ethoxycarbonyl) propyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1'-ethoxycarbonyl-3'-methylbutyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-bromobenzoate; 1 '- (ethoxycarbonyl)) - 2'-hydroxypropyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate; 1 ' -cyclo-carbonyl-ethyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-cyanobenzoate; 1 '- (ethoxycarbonyl) ethyl-5- (2,6-dichloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-6-bromo-4- (trifluoromethyl) phenoxy) -2-cyanobenzoate; and 1 '- (thioethylcarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate.

Compositions containing stereoisomers and optical isomers of the compounds of the above formula are also within the scope of the present invention.

The compounds of formula (I) may be prepared, for example, by reacting a substituted benzoyl halide of formula (II) with an alcohol M or a substituted hydroxy-carboxylic acid ester with formula (III) with a hydroxy group. , or an appropriately substituted benzoic acid derivative of formula (II) - M represents a hydroxy group - substituted by an alpha-halo carboxylic acid ester of formula (III) - Q halogen - according to methods known in the art, ), M and Q represent one halogen atom and the other hydroxyl group.

Benzoyl halides or benzoic acids and substituted α-hydroxy (or α-halo) carboxylic acid esters are commercially available or can be prepared by known methods.

In a preferred embodiment of the process of the invention, at least a stoichiometric amount of substituted benzoyl halide is added to the substituted α-hydroxycarboxylic acid, preferably an acid acceptor such as triethylamine, pyridine, Ν, Ν, while stirring. in the presence of dimethylaniline. Since an exothermic reaction typically occurs, the substituted benzoyl halide is added portionwise so that the temperature of the reaction mixture does not rise excessively above 35 ° C.

When the compounds of formula (I) are prepared by reacting a substituted benzoic acid with an alpha-halocarboxylic acid ester, preferably the latter is added to the former, an azo compound such as 1,5-diazobicyclo [5.4.0] undec- 5 (DBU) in the presence. Whichever synthesis route is chosen, the reaction may be carried out, if desired, in the presence of an inert solvent such as benzene, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran and the like. After the addition of the substituted benzoylialealide to the o-hydroxycarboxylic acid ester (or the α-halocarboxylic acid ester substituted benzoic acid), the reaction mixture is heated to reflux and refluxed until the desired degree of conversion is achieved. . The reaction mixture is cooled to room temperature, washed successively with dilute acid, dilute base and water and the phases are allowed to separate. The substituted diphenyl ether may be recovered from the organic phase by any known means, such as evaporation, crystallization, drying under vacuum or the like. If desired, the substituted diphenyl ether product may be further purified, for example by recrystallization.

I-XII below. Examples 1 to 6 illustrate the preparation of specially substituted diphenyl ether derivatives. Example I Preparation of Ethoxycarbonyl-ethyl 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate

1.18 g (0.01 mol) of ethyl lactate and 0.79 g (0.01 mol) of pyridine in 30 ml of benzene are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. 3.79 g (0.01 mol) of 5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzyl chloride in 20 ml of benzene are added dropwise with stirring at room temperature (about 20 ° C). Exothermic warming is observed. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 6 hours. The reaction mixture is cooled, transferred to a separatory funnel and washed successively with 30 ml of hydrochloric acid, water, n-sodium hydroxide solution and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. This gives 2.89 g of 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethyl / phenoxy) -2-nitrobenzoate as a clear, oily substance.

MMR (acetone, D ₆ ) 7.2-8.30 (complex multiplet, 611), 5.35 y (quartet, H), 4.28 δ (quartet, 2H), 1.62 δ (doublet, 3H), 1.25 δ (triplet, 3H).

II. Example 1 Preparation of 1 '- (ethoxycarbonylmethyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate

1.32 g (0.01 mol) of ethyl 3-hydroxybutyrate and 1.1 g (0.01 mol) of triethylamine are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. 30 ml of benzene. 3.69 g (0.01 mol) of 5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoyl chloride (20 ml) are added dropwise to the solution at room temperature (about 20 ° C). benzene. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 6 hours. The reaction mixture was cooled, transferred to a separatory funnel and washed successively with 30 ml of n hydrochloric acid, water, n sodium hydroxide solution and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 3.75 g of 1 '- (ethoxycarbonylmethyl) ethyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate are obtained in the form of a brown oil.

MMR (acetone, d ₆ ): 7.2-8.3 δ (complex multiplet, 6H), 5.5 δ (quartet, 1H), 4.15 δ (quartet, 2H), 2.75 δ ( doublet, 2H), 1.3 δ (doublet, triplet, 6H).

III. example

Preparation of 2 '- (ethoxycarbonyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) 2-nitrobenzoate

Into a 250 mL 3-necked flask with a reflux condenser and magnetic stirrer was added 2.70 g (0.03 mol) of 3-hydroxypropionic acid and 2.38 g (0.03 mol) of pyridine in 110 mL of methylene chloride. 11.37 g (0.03 mol) of 5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoyl chloride (30 ml) are added dropwise to the solution at room temperature (about 20 ° C). in methylene chloride, Exothermic warming is observed. After completion of the addition, the reaction mixture was heated to reflux and refluxed for 22 hours. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 11.8 g of 2'-ethoxycarbonyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate are obtained in the form of a viscous, yellow oil.

MMR (acetone d ₆ ): 7.2-8.4 δ complex multiplet, 6H), 4.3 δ (triplet, 2H), 2.67 δ (triplet, 2H),

ARC. example

Preparation of 2 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate

To a 100 ml 3-necked flask with a reflux condenser and magnetic stirrer was added 20 ml of ethanol and 5 ml of pyridine in 30 ml of methylene chloride. To the solution, while stirring at room temperature (about 20 ° C), 2 '- (chlorocarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) (2.26 g, 0.005 mol) was added dropwise. - 2-nitrobenzoate in 15 ml of n-ethylene chloride. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 42.5 hours. The reaction mixture was cooled and concentrated in a rotary evaporator at 55 ° C. The residue is taken up in 100 µl of methylene chloride, transferred to a separatory funnel and washed successively with 30-30 ml of n hydrochloric acid, water, 7% aqueous ammonium hydroxide solution and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 1.3 g of 2 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitro benzoate are thus obtained in the form of a yellow oil.

NNR spectrum (chloroform): 7.0-8.1 δ (multiplet, 6H), 4.3 δ (multiplet, 4H), 2.65 δ (triplet, 211), 1.3 δ (triplet, 3H).

Example V Preparation of '- (ethoxycarbonyl) methyl-5- (2-chloro-4- / trifluoromethylphenoxy) -2-nitrobenzoate

1.25 g (0.012 mol) of ethyl glycolate and 0.80 g (0.01 mol) of pyridine in 35 ml of methylene chloride are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. 3.79 g (0.01 mol) is added dropwise to the solution while stirring at room temperature (about 20 ° C).

5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzyl chloride in 20 ml of methylene chloride. We observe an exotherm. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 42.5 hours. The reaction mixture was cooled, transferred to a separatory funnel and washed successively with 30 mL of 30 N hydrochloric acid, water, 7% aqueous ammonium hydroxide, and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 3.5 g of 1 '- (ethoxycarbonyl) methyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate are thus obtained in the form of a yellow oil.

MMR (chloroform): 7.0-8.4 δ (multiplet, 6H), 4.82 δ (singlet, 2H), 4.25 S (quartet, 2H), 131 δ (triplet, 3H).

VI. Example 1 Preparation of 'ethoxycarbonyl-2'-oxopropyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate

3.61 g (0.01 mol) of 5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoic acid are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. and 1.53 g (0.01 mol) of 1,5-diazobicyclo [5.4.0] undec-5-ene (DBU) in 50 ml of benzene. Ethyl 2-chloroacetoacetate (1.65 g, 0.01 mol) was added at room temperature (about 20 ° C) with stirring. The reaction mixture was then heated to reflux and refluxed for 20.5 hours. The reaction mixture is cooled, transferred to a separatory funnel and washed successively with 30 ml of n-hydrochloric acid, water, 7% aqueous ammonium hydroxide, and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 3.1 g of 1'-ethoxycarbonyl-2'-oxopropyl-5- (2-chloro-4-trifluoromethylphenoxy) 2-nitrobenzoate are obtained in the form of a brown oil.

MMR (acetone, d / _e ): 7.2-8.2 δ (multiplet, 6H), 5.8 δ (singlet, 1H), 4.2 δ (quartet, 2H), 2.3 δ (singlet) , 3H).

VII. example

Preparation of Xethoxycarbonyl) butyl 5- (2-chloro-4- (trifluoromethyl / phenoxy) -2-nitrobenzoate

3.61 g (0.01 mol) of 5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoic acid are charged into a 100 ml 3-necked flask with a reflux condenser and a magnetic stir bar. and 1.53 g (0.01 mol) of DBU in 50 ml of benzene. Ethyl 2-bromo-valerate (2.19 g, 0.01 mol) was added to the solution with stirring at room temperature (about 20 ° C). The reaction mixture was heated to reflux and refluxed for 22 hours. The reaction mixture was cooled, transferred to a separatory funnel and washed successively with 30-30 mL of n hydrochloric acid, water, 7% aqueous ammonium hydroxide, and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C to give 2.2 g of 1 '- (ethoxycarbonyl) butyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro Benzoate is obtained in the form of a brown oil.

MMR (acetone, d ₆ ): 7.2-8.2 δ (multiplet, 6H), 5.25 δ (triplet, 1H), 4.28 δ (quartet, 2H), 0.8-1. 9 δ (multiplet, 10H).

VIII. EXAMPLE 1 Preparation of '- (phenoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethyl / phenoxy) -2-nitrobenzoate

3.61 g (0.01 mol) of 5- (2-chloro-47-trifluoromethylphenoxy) -2-nitrobenzoic acid and 1.53 g are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. g (0.01 mol) of DBU in 50 ml of benzene. Phenyl 2-bromoacetate (2.29 g, 0.01 mol) was added at room temperature (about 20 ° C) with stirring. The reaction mixture was heated to reflux and refluxed for 22.5 hours. The reaction mixture is cooled, transferred to a separatory funnel and washed successively with 30 mL of n hydrochloric acid, water, n sodium hydroxide solution and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. This gives 2.58 g of 1 '- (phenoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate as a light green syrupy liquid.

MMR (acetone, d _e ): 7.0-8.25 δ (multiplet, 11H), 5.5 δ (quartet, 1H),

1.68 δ (doublet, 3H).

IX. Example 2 Preparation of '- (ethoxycarbonyl) propyl-5- (2-chloro-4- / trifluoromethyl / phenoxy) -2-nitrobenzoate

3.61 g (0.01 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoic acid and 100 ml of a 3-necked flask, fitted with a reflux condenser and a magnetic stirrer were charged. 53 g (0.01 mol) of DBU in 35 ml of benzene. Ethyl 2-bromobutyrate (1.95 g, 0.01 mol) in benzene (15 ml) was added dropwise at room temperature (about 20 ° C) with stirring. Exothermic warming is observed. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 24 hours. The reaction mixture was cooled, transferred to a separatory funnel and washed successively with 30 mL of 30 mL of n hydrochloric acid, water, 7% aqueous ammonium hydroxide, and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 1.2 g of l '- (ethoxycarbonyl) propyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate are thus obtained in the form of a light brown syrupy liquid.

MMR (acetone, d ₆ ): 7.2-8.2 δ (multiplet, 6H), 5.15 δ (triplet, H), 4.2 δ (quartet, 2H), 1.9 δ (quartet) , 2H), 0.8-1.3 δ (average ____ T-shirt triplets, 6H).

Example X Preparation of 'ethoxycarbonyl-3'-methylbutyl-5- (2-chloro-4-trifluoro-41-methylphenoxy) -2-nitrobenzoate

1.60 g (0.01 mole) of ethyl α-hydroxyisocaproate and 0.79 g (0.01 mole) of pyridine are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic plug. 40 ml of methylene chloride. To this solution, while stirring at room temperature (about 20 ° C), is added dropwise 5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoyl chloride (3.79 g, 0.01 mol) in methylene chloride (10 ml). chloride. Exothermic warming is observed. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 46.5 hours. and wash with water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 1.99 g of 1'-ethoxycarbonyl-3'-methyl-butyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate are obtained in the form of a viscous brown oil. .

MMR (acetone, d ₆ ): 7.2-8.3 δ (multiplet, 6H), 5.2 δ (triplet, 1H), 4.2 δ (quartet, 2H), 1.8 δ (multiplet) , 3H), 0.8-1.4 δ (multiplet, 9H).

XI. Example 2 Preparation of r-ethoxycarbonyl-2'-hydroxy-propyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate

19.56 g (0.04 mol) of l'-ethoxycarbonyl-2'-oxopropyl-5- (2-chloro-4) is added to a 500 ml 3-necked flask with a reflux condenser and a magnetic stirrer. - (trifluoromethyl) -phenoxy) -2-nitrobenzoate (prepared as described in Example VI) in 100 ml of methanol. 3.14 g (0.05 mol) of sodium cyanoborohydride and a few drops of methyl orange indicator are added to the solution while stirring at room temperature (about 20 ° C). Then a 75:25 by volume solution of 2N hydrochloric acid and methanol was added dropwise at such a rate that the color of the indicator remained unchanged. The reaction mixture was heated to reflux and refluxed for 20 hours. The reaction mixture was cooled and packed in a rotary evaporator at 55 ° C. The concentrated residue is taken up in 200 ml of diethyl ether, transferred to a separatory funnel and washed successively with 100 ml of n hydrochloric acid, water, n sodium hydroxide solution and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 18.1 g of 1'-ethoxycarbonyl-2'-hydroxypropyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate are thus obtained in the form of a yellow syrupy liquid.

MMR (acetone, d ₆ ): 7.2-8.3 δ (multiplet, 6H), 4.2 δ (multiplet, 3H), 3.2 δ (quartet, 2H), 1.3 δ (triplet) overlay doublet, 5H).

XII. Example 1 Preparation of 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-bromobenzoate

1.18 g (0.01 mol) of ethyl lactate and 0.79 g (0.01 mol) of pyridine in 50 ml of methylene chloride are added to a 100 ml 3-necked flask with a reflux condenser and a magnetic stirrer. 2.07 g (0.005 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-bromobenzoyl chloride in 10 ml of methylene chloride are added dropwise at room temperature (about 20 ° C) with stirring. Exothermic warming is observed. After the addition was complete, the reaction mixture was heated to reflux and refluxed for 66 hours. The reaction mixture was cooled, transferred to a separatory funnel and washed successively with 30-30 mL of n hydrochloric acid, water, 7% aqueous ammonium hydroxide, and water. The washed organic phase was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 2.2 g of 1 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-bromobenzoate are thus obtained in the form of a viscous, yellow syrup-like liquid. í

MMR (acetone, d ₆ ): 7.0-8.0 δ (multiplet,

611), 5.25 δ (quartet, 1H), 4.18 δ (doublet, 3H), 1.68 δ (doublet, 3H), 1.18 δ (triplet, 6H).

It has been found that formulations containing the compounds of formula I inhibit the growth of a number of undesirable plants, i.e. weeds, by applying herbicidal amounts to the soil prior to emergence of the weeds or after application to the weeds. The term " herbicidal amount " refers to an amount or composition of an active ingredient that damages the weed to such an extent that the weeds are unable to recover after application. The amount of active ingredient or mixture of active ingredients required to achieve the proper herbicidal activity may vary within wide limits and will depend on a number of factors such as the toughness of the weeds, the degree of weed infestation, weather conditions, soil conditions, application patterns and the like. The required amount of active compound or amount of active compound is generally between 0.19 kg / ha and 9.85 kg / ha. Of course, the effect of a formulation containing a particular active ingredient on a particular weed can be readily determined by laboratory or field experiments known in the art.

The compositions of the present invention contain the active ingredient of formula (I) and agriculturally acceptable excipients, such as inert carriers. The compositions of the present invention are used, for example, in the form of powders, granules, wettable powders, solutions, suspensions, aerosols, emulsions, dispersions and the like, as known in the art. The content of the active ingredient or the mixture of active ingredients in the compositions may vary within wide limits, from 0.05% to 95% by weight of the composition. The compositions generally contain from 5 to 75% by weight of the active ingredient.

We have found that the compositions of the present invention control a number of broadleaf and grass weeds,

191,024 hectares are applied at 1.97 kg or less per hectare before or after hatching, while not significantly affecting crop plants such as corn, wheat, rice and soybeans. Examples of weeds that can be controlled well with the compositions of the present invention include white mustard (Brassica kaber), yellow brushwort (Setaria glauca), fingerweed (Digitaria sanguinalis), senna (Sesbania spp.), Fluffy silkworm (Abutilon theophrasti), Sorghum halepense (Sorghum halepense). Echinochfoa crusgaili);

We have examined some of the I to XII. A herbicidal activity against certain weeds, under defined lighting, temperature and humidity conditions, is obtained using a composition comprising a compound of formula (I) prepared as described in Example 1A. Seeds of selected weeds were sown in crates. In the pre-emergence tests, the soil was treated with the formulations immediately after sowing. In post-emergence tests, the soil is germinated for two weeks! after a period of time. By spraying a solution of the active ingredients, the treatment was carried out according to the indicated amount of active ingredient. - weed growth stage of the weeds and periodically evaluated the toxicity of the preparation after ⁰ application.

The following table lists the weeds and the active ingredients of the formulations used, denoted by X, and referenced to the corresponding preparation examples. The formulations were applied before hatching at a rate of 1.97 kg of active ingredient per hectare.

weeds

I. II. III.

agent

ARC. V. VI. VII. VIII. IX. X

Sida spinosa Weevil White Mustard Yellow Brush Lawn Large Toad Sorghum halepense

Downy Silkworm Dawn Wild Oats Cocksfoot

X X x x

X

X X

X X

X X

X

X X

X X

X

X X

X X

X X

X X

X X

X X

X X

X X

X X

X X

X

X X

X X

X X

X X

X X

X X

X X

X X

X

X X

X X

X X

X

X X

X

X X

X X

X

X X

In each of the above experiments, it was observed that 21-22. day, the various weeds were either destroyed or damaged to such an extent that they could no longer be recovered.

The formulations containing the active compounds listed in the table below were applied after emergence to the indicated weeds at a rate of 1.97 kg of active ingredient per hectare.

weeds

I. II. III.

agent

ARC. V. VI. VII. VIII. IX. X

Sida spinosa Weevil White Mustard Yellow Brush Lawn Large Toad Sorghum halepense

Fluffy silk sweater

Morning glory

Wild oats

Barnyardgrass

cocklebur

X

X

X

X

X

X

X

X

X

X

X

X

X

X X

X X

X

X X

X X

X X

X X

X X

X

X X

X

X X

X X

X X

X

X X

X

X X

X X X

X

X X

X X

X X

191 024

During the experiments it was observed that 21-22 after application of the preparation. days, the weeds have died or been damaged to such an extent that they lead to death.

It has been observed that formulations containing compounds of formula (I) other than nitro-powder, e.g. less than 4.9 kg active ingredient per hectare, for example 1.97 kg active ingredient or less. Those preparations j ar _3, containing (I) active compound of formula in which the nitro group is, in general, both before emergence and after emergence applied effective ha, 1.97 kg or less active substance quantities.

The herbicidal activity of the compounds of the present invention was compared with that of known compounds in experiments.

Test compounds

N-1-ethoxycarbonyl-ethyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate;

B1 sec-butyl 5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate.

Compounds A / B were dissolved in a 90: 8: 2 by volume mixture of acetone in methanol: diethyl formate and treated with a variety of weeds for the pre-emergence and post-emergence herbicidal activity under the same laboratory light, temperature and humidity conditions.

The results of the tests are presented in the following tables.

Table 1

Herbicidal activity of Compounds A / B on day 13 after pre-emergence treatment with 0.49 kg / ha of active compound

Compound A Compound B A-I A-2 (retest) B-1 B-2 (retest) Plant NIR ^X PRR ^X NIR PRR NIR PRR NIR PRR

TEAW 9 No, R 8 No, R 5 R, No. 2 Not JMWD 10 Not 10 Not 0 0 MSTD 9 No, Y, R 10 Not 7 Ne.R 5 Not COFEE. 7 No, R 7 No, R 6 RJH, Do 2 R VTLF- 3 No, R 5 R, Ne 2 No, R 1 Not MNGY 7 No, R 4 R Second R 0 YNSG 3 Not 2 No, R 0 0 YLFX 10 Not 9 No, R, H 8 No, R 5 HNE, R CBGS 9 RH Do 10 Not 9 R, H 9 R, Ne JNGS 9 Ne.RJH 9 No, R, H 5 R, H 7 H, R) 9e WOAT 3 R 0 7 From H, R 1 R BNGS 9 No, R 8 No, R 7 From H, R 5 H.RjMe

^X NIR: Quantity of injury ^X PRR: Physiological effect

191 024

II. Spreadsheet

Herbicidal activity of Compounds A / B on day 22 after pre-emergence treatment with 0.49 kg / ha formulation

Plant Compound A Compound B A-1 A-2 (retest) B-1 B-2 (retest) NIR PRR NIR PRR NIR PRR NIR PRR TEAW 8 No, R 8 Not 0 0 JMWD 8 No, Y, R 10 Not 0 0 MSTD 10 Not 10 Not 0 0 COFEE 6 No, R 7 No, R 2 Not 3 No, RJ4 VTLF 5 R 6 R 0 0 MNGY 7 No, R 3 No, R 0 0 YNSG 1 Cl 1 cl 0 0 YLFX 10 · - No. 9 NeJI.R 6 H.R 1 R CBGS 8 R, No. 9 E, R 8 R 9 R, No. JNGS 9 From H, R 9 No, H, R 4 No, R 4 No, R WOAT 0 1 H 5 From H, R 1 R BNGS 10 Not 8 H, Do 5 Not 0

III. Spreadsheet

Herbicidal activity of Compounds A / B on day 13 after hatching treatment with 0.24 kg / ha formulation

Plant Compound A Compound B THE 2 A-2 (retest) B-1 B-2 (retest) NIR PRR NIR PRR NIR PRR NIR PRR TEAW 8 Do / R 8 Do / R 6 No, R, Z 6 No, Z, R JMWD 10 Not 10 Not 9 No, Y, R 8 No, Z, R MSTD 10 Not 10 Not 8 No, Z, R 8 No, Z, R COFEE 10 Not 10 Not 8 Do / R 8 Do / R VTLF 10 Not 10 Not 10 Not 8 No, Z, R MNGY 9 Not 10 Not 6 No, R / 5 No, R / YNSG 0 0 0 0 YLFX 8 H, Ne, R 7 NeJl.R 3 Not 3 H, Do WOAT 5 R, Ne 3 R, H 3 R 0 BNGS 9 No, R 8 No, R, H 7 No, R 5 No, R COTN 7 No, R 7 No, R 5 No, R 6 No, R

191 024

ARC. T b b 1 z a t

A / and P. ' - herbicidal effect of the compound on the 22nd day after hatching treatment with the product containing 0.24 kg / ha

A / compound B / compound • A-1 A-2 (repeated B-1 B-2 (repeated i test) test) Plant NIR PRR NIR PRR NIR PRR NIR PRR TEAW 8 No, R / 8 No, R, Z 4 R, Ne 4 No, R, Z JMWD 10 Not 10 Not 9 No, R 8 Not MSTD 10 Not 10 Not 7 No, R, Z 7 No, R COFEE 9 No, R, Z 10 Not 7 No, R, Z 6Ne, R / VTLF 10 Not 10 Not 10 Not 8 No, R7 MNGY 9 No, R, Z 10 Not 6 No, R, Z 3 No, Z YNSG 0 0 0 0 YLFX 6 Ne.H.R 6 Not 4 Not 3 Not WOAT 3 Not 0 2 R, Ne 1 Not BNCS 8 No, R 7 Not 6 R.Ne.Cl 5 No, R COTN 6 No, R 5 No, R 4 No, R 3 No, R

LEGEND

Designation Plant variety

BNGS barnyardgrass (Echinoclrloa crusgalli) CBGS big toad (Digitaria sanguinalis) COFEE senna (Daubentonia punicea /Cav./ D.C.) COTN cotton (Gossypium hirsutum) JMWD datura (Datura stramonium) JNGS Sorghum halepense MNGY morning glory (Ipomoea purpurea Roth) MSTD white mustard (Brassica kaber /D.C./) TEAW Sida spinosa VTLF fluffy silk (Abutilon theophrasti) WOAT wild oats (Avena fatua) YLFX yellow brush lawn (Setaria glauca) YNGS (Cyperus esculentus)

Indication of the degree of physiological effect

Cl = chlorosis E = decreased hatching H = 2,4-D type hormone activity Ne = necrosis R = delayed growth Y = late germination Z = regrowth

PATENT CLAIMS

Claims (10)

A process for the preparation of diphenyl ether derivatives wherein, in the general formula (I): - A represents a halogen, cyano or nitro group, - X represents a hydrogen or halogenate, - Y represents a hydrogen or halogen atom, or cyano, trifluoromethyl or Represents a C 1-4 alkyl group, - Z represents oxygen or sulfur, - C1-C3 alkylene optionally monosubstituted with C1-4 alkyl, oxoalkyl or hydroxyalkyl, and - R * represents hydrogen, C1-10 alkyl; C3-C8 cycloalkyl, an agriculturally acceptable ion or phenyl optionally mono-, di- or tri-substituted with halo, C1-C10 alkyl or alkoxy, cyano, nitro or trifluoromethyl, 4Q wherein (II) benzoyl halide of formula (III) a-hidroxikarborsav ester - one of A, X, Y, Z, R and R ¹ are as defined above, M and Q are halogen and the other hydroxyl group. (Priority: August 08, 1980) 45 A process according to claim 1 for the preparation of diphenyl ether derivatives having the following formula: wherein: - A is halogen, cyano or nitro, - X is hydrogen or halogen, - Y is halogen, 50 - Z is oxygen or sulfur, - R 1-3 alkylene, and R ^{1 is} C 1 -C 10 alkylene or C 3 -C 8 cycloalkyl, characterized in that the starting materials used in the formulas II and III are M halogen and Q is hydroxy and A, X, Y, Z , R and R * are as defined herein. (Priority: August 10, 1979) 3. A process according to claim 1 for the preparation of diphenyl60 'ether derivatives having the following general formula (1): - A halogen, cyano or nitro group; - X is hydrogen or halogen, - Y is hydrogen, cyano, trifluoromethyl or C1-C4 alkyl, - Z is oxygen or sulfur, - R is alkylene monosubstituted with C 1-3 -C 1-4 alkyl, oxoalkyl or hydroxyalkyl, and - R * represents a hydrogen atom, an agriculturally acceptable ion, a phenyl group or a phenyl monodi- or tri-substituted with a C 1 -C 10 alkyl or alkoxy group, a balogen atom, a cyano, a nitro or a trifluoromethyl group, characterized in that starting materials are used , wherein A, X, Y, Z, R, R ^{1 in} the formulas (II) and (III) have the meanings given in cubic, and Q and M have the meaning given in claim 1, (Priority June 27, 1980) A process for the preparation of diphenyl ether derivatives according to claim 1, wherein Λ, X, Y, Z and R in the general formula (I) have the meaning given in claim 2 and R ^{1 represents a C} 1-4 alkyl group, characterized in that starting materials wherein A, X, Y, Z, R and R ^{1 in} the formulas (II) and (III) are as defined in the foregoing, and Q and M are as defined in claim 2. (Priority: August 10, 1979) A process for the preparation of diphenyl ether derivatives according to claim 1, wherein A, X, Y, Z and R in the general formula (I) have the meaning given in claim 3 and R ^{1 represents a C} 1 -C 4 alkyl group. starting materials having the formulas II, III, A, X, Y, Z, R and R ^{1 are} as defined above, and M and Q are as defined in claim 1. (Priority: June 27, 1980) 6. The method of claim 1 characterized in that diphenyl ether derivatives having formula (I) wherein A is nitroesoportot, X is hydrogen, Z is oxygen and Y is halogen and R and R ¹ are as defined in claim 1., characterized in that a used as the starting materials having formula (II) wherein (III), X, Z, Y, R and R ¹ in the scope, QésM are as defined in claim 1 meanings. (Priority: August 08, 1980) The process for the preparation of diphenyl ether derivatives according to claim 1, wherein A in the formula (I) is selected from the group consisting of nitro, X is hydrogen, Z is oxygen and Y is halogen, and R and R * are as defined in claim 2. starting materials wherein A, X, Y, Z, R and R ^{1 in} the formulas (II) and (III) are as defined above, Q and M are as defined in claim 2. (Priority: August 10, 1979) 8. The method according to claim 1 characterized in that diphenyl ether derivatives thereof, mean Λ nitroesoportot, X is hydrogen, Z is oxygen and Y is a halogen atom having formula (I) wherein R and R ¹ as defined in claim 3 meanings, characterized in that a starting materials of formula (II) and (III), X, Y, Z, R and R ¹ are within the scope of the invention, Q and M are as defined in claim 1. (Priority: June 27, 1980) The process of claim 1, 1 '- (ethoxycarbonylmethyl) ethyl-5,2-chloro-4- (trifluoromethylphenoxy) -2-nitrobenzoate; 2 '- (ethoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) methyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1'-ethoxycarbonyl-2'-oxopropyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) butyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (phenoxycarbonyl) ethyl-5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; 1 '- (ethoxycarbonyl) propyl 5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoate; r -Ethoxycarbonyl-3'-methyl-butyl-5- (2-chloro-4- (trifluoromethyl) -phenoxy) -2-nitrobenzoate; 1 '-ethoxycarbonyl2'-hydroxypropyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoate; or l '- (ethoxycarbonyl) ethyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-bromobenzoate, employing the appropriate starting materials. (Priority: June 27, 1980) 10. Herbicidal formulations, characterized in that they contain from 5% to 75% by weight of diphenyl ether sararin azole as active ingredient, in which: - A represents a halogen, cyano or nitro group, - X represents a hydrogen or halogen atom, - Y represents hydrogen or halogen, or cyanotrifluoromethyl or C 1-4 alkyl, - Z represents oxygen or sulfur, - R 1-4 optionally monosubstituted with C 1-4 alkyl, oxoalkyl or hydroxyalkyl and - R ¹ is hydrogen, C 1 -C 10 alkyl, C 3 -C 8 cycloalkyl, agriculturally acceptable ion, phenyl or halo, C 1 -C 10 alkyl-;