SK6593A3 - New herbicides - Google Patents

Abstract

4-Benzoylisoxazole derivative of general formula (I): <CHEM> wherein: R<1> represents an alkyl group or an optionally substituted cycloalkyl group R<2> represents a halogen atom, or a group selected from R<5>, -OR<5>, -S(O)mR<5>, -O(CH2)q-OR<5>, -CO2R<5> and nitro; R<3> represents a halogen atom, or a group selected from R<5>, -OR<5>, -S(O)mR<5> and -O(CH2)q-OR<5>; R<4> represents a hydrogen or halogen atom, or a group selected from R<5>, -OR<5>, -S(O)mR<5>, -O(CH2)q-OR<5> and nitro; with the proviso that at least one of the groups R<2>, R<3> and R<4> represents -O(CH2)q-OR<5>; R<5> represents a straight- or branched- chain alkyl group containing from one to four carbon atoms optionally substituted by one or more halogen atoms; m represents zero, one or two; and q represents an integer from one to three;. and their use as herbicides is described.

Description

Technical field

The present invention relates to novel 4-benzoylisoxazole derivatives, compositions containing them and their use as herbicides.

BACKGROUND OF THE INVENTION

Herbicidal 4-benzoylisoxazoles are described in published European patent application 0418175.

SUMMARY OF THE INVENTION

The present invention provides 4-benzoylisoxazole derivatives of formula (I)

in which

R ¹ represents a straight or branched alkyl group having 1 to 4 carbon atoms or a 3- or 4-membered cycloalkyl group optionally substituted by a straight or branched alkyl group containing up to 4 carbon atoms,

E- represents a halogen atom or a group selected from the group consisting of P. ⁵ , -OR ⁵ , -S (O) mR ⁵ , -O (CH 2) R -OR ⁵ , -CO 2 R ^5, and nitro,

R ³ represents a halogen atom or a group selected from the group

I. 'L:

including R ⁵ , -OR ⁵ , -S (O) _m R ^5, and -

-O (CH 2) q -OR 5,

R ⁴ represents a hydrogen or halogen atom or a 'group chosen from R ^5, -OR ⁵ _T is the

-S (O) m R ⁵ , -O (CH 2) »-OR ⁵ and a nitro group, with the proviso that at least one of R ² , R ³ , and R ⁴ is -O (CH 2) ) <»- 0R ⁵

R ⁵ represents a straight or branched alkyl group having 1 to 4 carbon atoms, which is optionally sub-;

substituted with one or more halogen atoms, J m is zero, 1 or 2 and i;

• ŽŽ q represents an integer from 1 to 3.i;

ί> b w

The compounds of the invention show unexpected;

and, with respect to known compounds, a high herbicidal activity against serious weed species, including Xanthium strumarium.

Preferred compounds of the invention are those compounds of formula I wherein R ³ is -O (CH 2) »-OR ⁵ .

A preferred group of compounds according to the invention with respect to their herbicidal properties are those of the formula I in which:

R ² represents a hydrogen atom or a group selected from the group consisting of R ^5, -OR ^5, -S (0) _m R ^5, -CO 2 R ⁵ group, a nitro, Others

R ³ represents -O (CH 2) q-0R ^5,. ' and

R ⁴ represents a hydrogen or halogen atom or a group?

selected from the group consisting of R ⁵ , -OR ⁵ , R -S (O) _m R ^5, and nitro a11

q means 2 or 3. '

Another preferred group of compounds of formula I with respect to their herbicidal properties are those which are>

Have one or more of the following:

R 1 represents a methyl group, a stylish group, a 1-methylethyl group, a cyclopropyl group or a 1-methylcyclopropyl group,

R 2 is chlorine, bromine or fluorine atom or a group selected from the group consisting of R ^5, and -S (0) _m R ^5,

R ⁴ is chlorine, bromine or fluorine atom or a group selected from the group consisting of R ⁵ and -S (O) _m R ^a,

^R represents straight-chain or branched alkyl having 1 to 4 carbon atoms, optionally substituted by one or more halogen atoms.

Another preferred group of compounds of formula I with respect to their herbicidal properties are compounds having one or more of the following features:

R 1 is 1-methylethyl, 1-methylcyclopropyl or cyclopropyl,

R ⁵ is methyl, ethyl or three fluoromethyl, at least one of R ² and R ⁴ is -SO 2 CH 3, provided that R ² and R ⁴ do not simultaneously represent -SO 2 CH 3, g is 2.

A particularly preferred group of compounds of the formula I in view of their herbicidal properties are those of the formula I in which:

R ¹ represents a cyclopropyl group,

R ² is chlorine, bromine or fluorine atom or a group selected from the group consisting of methyl, tri f dimethylurea hunting group and a group -SíOmCHa,

R ³ represents -O (CH 2) q-OR ^a,

R ⁴ represents a chlorine atom, a bromine atom or a fluorine atom or a group selected from the group consisting of methyl, trifluoromethyl and -S (O) mCH 3, at least one of R ² and R ⁴ being -S (O) _m CH 3 provided .

f 'ι iľ i

R ² and R ^{4 are} not -SO 2 CH 3 and q is 2.

Particularly preferred compounds of the invention with respect to their herbicidal activity are those selected from the group consisting of:

1. 4- / 2,4-dibromo-3- (2-methoxyethoxy) benzoyl-5-cyclopropylisoxazole;

2. 4- [2-Bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] -5-cyclopropylisoxazole;

3. 4- (2-Bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -5- (1-methylcyclopropyl) isoxazole;

4. 4- [2-Bromo-3- (2-methoxyethoxy) -4-methylsulphonylbenzoyl] methylisoxazole;

5. 4- [2-Chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] -5-cyclopropylisoxazole;

6. 4- (2-Chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -5-isopropylisoxazole,

7. 4- (2-Chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -5-methylisoxazole>

8. 4- / 2-Bromo-3- (2-methoxyethoxy) -4-methylsulfenylbenzoyl-5-cyclopropylisoxazole;

9. 4- / 2-Bromo-3- (2-methoxyethoxy) -4-methylsulphinylbenzoyl-5-cyclopropylisoxazole;

10. 4- [4-Bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoyl] -5-cyclopropylisoxazole;

11. 5-cyklopropy1-4- / 2-metylsulfény1-3- (2-methoxyethoxy) - bens : Oy1 / isoxazol, 1 12th 5-cyclopropyl-4- / 2-metylsulíiny1-3- (2-methoxyethoxy) - ben: joyl / isoxazole and

3. 5-Cyclopropyl-4- (2-methylsulfonyl-3- (2-methoxyethoxy) benzoyl) isoxazole.

Under the numbers assigned to each compound in the above list, these compounds are also listed in the following section.

Compounds of formula (I) may be prepared using procedures or modified forms thereof (i.e., procedures described herein or in the literature), for example, procedures that will be described below.

In the following description of the process for preparing the compounds of the invention, the general symbols in the general formulas are not specifically defined and are to be understood as having the above defined meanings that are consistent with the first definition of each symbol in the specification.

It will be appreciated that in the descriptions of the following methods, the sequence of the reaction steps may be performed in different order, and appropriate protecting groups may be used to obtain the desired compounds.

According to one embodiment of the invention, compounds of formula I may be prepared by reacting a compound of formula II,

R2. 0 0

L wherein R ¹ , R ² , R 3 and R ⁴ are as defined above and L represents a leaving group, from a hydroxylamine salt. Typically, the preferred hydroxylamine salt is hydroxylamine hydrochloride. Usually L represents an alkoxy group, for example an ethoxy group, or an N, N-dialkylamino group, for example a dimethylamino group. This reaction is usually carried out in a solvent such as ethanol or acetonitrile, optionally in the presence of a base-binding agent or an acid such as triethylamine or sodium acetate.

According to another embodiment of the invention, compounds of formula I may be prepared by reacting a compound of formula III,

(III) wherein R ¹ is as defined above, with a compound of formula IV,

(IV) wherein R ² , r 5 and R ⁴ are as defined above. This reaction is usually carried out in the presence of a Lewis acid catalyst, for example in the presence of aluminum chloride, at a temperature between ambient temperature and 100 ° C.

According to another embodiment of the invention, the compounds of formula I may be prepared by reacting a compound of formula V, (V)

Y

Wherein R ¹ is as defined above and Y represents a carboxy group or a reactive derivative thereof (such as a carboxylic acid chloride or a carboxylic acid ester) or a cyano group, with an appropriate organometallic reagent such as a Grignard reagent or an organclite reagent. This reaction is usually carried out in an inert solvent such as ether or tetrahydrofuran at a temperature of from 0 ° C to the reflux temperature of the reaction mixture.

The intermediates used in the preparation of the compounds of the formula I according to the invention can be prepared using known methods or modified forms thereof.

Compounds of formula II may be prepared by reaction of a compound of formula VI,

R ² 0 0 r ³ > || ^K (VI) R ⁴ wherein R ¹ , R ² , R ³ and R ⁴ have the meanings defined above, either with trialkyl orthoformate, how is triethyl orthoformate, or

with dimethylformamide dialkylacetal such as dimethylformamide dimethyl acetal. Said reaction with triethyl orthoformate is usually carried out in the presence of acetic anhydride at the reflux temperature of the reaction mixture, whereas the reaction with dimethylamidium dialkyl acetal is optionally carried out in the presence of an inert solvent at a temperature from ambient to reflux. condenser.

The reaction is usually carried out in the presence of an organic base such as triethylamine in an inert solvent such as toluene or dichloromethane at a temperature of from -20 ° C to ambient temperature.

Compounds of formula (VI) may be prepared by reaction of an acid chloride of formula (VII),

COC1

(VII) wherein R ²

R ³ and R ⁴ are as defined above, with a metal salt of a compound of formula VIII, (VIII)

OtBu wherein R ¹ is as defined above to form a compound of formula IX wherein R 1, R 2

R ³

(IX) and R ⁴ are as defined above.

which is subsequently decarboxylated to give a compound of formula VI. The reaction in which Ba obtains a compound of formula IX is usually carried out in a solvent such as an alcohol, preferably methanol, in the presence of a metal, preferably magnesium. The decarboxylation is usually carried out by heating the compound of the formula IX to reflux;

in the presence of a catalyst such as paratoluene- [sulfonic acid] in an inert solvent such as toluene.

Intermediates of formulas III, IV, V, VII and VIII are known compounds or can be prepared using known procedures or modified forms thereof.

J; It is known to one skilled in the art of organic chemistry

That some compounds of formula I may be prepared by interconversion of other compounds of formula I and such;

interconversions are also included within the scope of the invention. Examples of such interconversions are described below.

s

According to another embodiment of the invention, the compounds may be compounds;

according to the invention, wherein m is 1 or 2, prepared by oxidation of the sulfur atom of compounds wherein m is zero. This!

The oxidation of the sulfur atom is usually carried out, for example, by using 3-chloroperoxybenzoic acid in an inert solvent, such as dichloromethane, at a temperature of from -40 ° C to ambient temperature. j

In the following, the invention will be explained in more detail by way of examples of a specific embodiment thereof, these examples being for the purpose of illustration only and are not to be construed as limiting the scope of the invention as defined by the claims. The examples show the preparation of the compounds of formula I and the reference examples show the intermediates of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

To a stirred mixture of 3-cyclopropyl-2-ethoxymethylene-1- (2-bromo)

Sodium acetate (1.77 g) was added to 3- (2-methoxyethoxy) -4-methylsulfonylphenyl / propane-1,3-dione (8.5 g) and hydroxylamine hydrochloride (1.77 g) in ethanol. The resulting mixture was stirred overnight at ambient temperature and then evaporated to dryness. The residue was dissolved in ethyl acetate and washed with water, dried over magnesium sulfate and filtered. The filtrate is then evaporated to dryness. The residue is chromatographed on silica gel, eluting with ethyl acetate / cyclohexane (1: 5) to give 4- (2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -5- from the appropriate eluate fraction. cyclopropylisoxazole (compound 2) as a yellow oil.

Yield: 3.3 g, nuclear magnetic resonance spectrum:

(CDCl3) 1.3 (2H, m), 1.4 (2H, m), 2.6 (1H, m), 3.3 (3H, s), 3.5 (3H, s), 3, 9 (2H, m), 4.5 (2H, m), 7.3 (1H, d), 8.1 (1H, d), 8.15 (1H, s).

Using an analogous procedure, the compounds of formula (I) shown in the following table are prepared.

clay

Zltíče nina č. R ¹ R ² R ³ R ⁴ Melting point / NMR 1 Cp br O (CH ₂ ) ₂ OMe br 1.15 (2H, m) 1.3 (2H, m) 2.5 (1H, m) 3.4 (3H, s) 3.75 (2H, t) 4.1 (2H, t) 6.8 (1H, d) 7.5 (1H, d) 8.1 ( H, s) 3 1-Me-Cp br O (CH ₂ ) ₂ OMe SO ₂ Me 0.9 (2H, m) 1.4 (3H, s) 3.4 (3H, s); 4.4 (2 H, t) 7.2 (1 H, d) 8.0 (1 H, s) 8.1 (1 H, d) 4 Me br O (CH ₂ ) ₂ OMe SO ₂ Me 2.6 (3H, s) 2.0 (3H, s) 3.45 (3H, s); 3.8 (2H, t); 4.4 (2 H, t) 7.2 (1 H, d) 8.0 (1H, d) 8.1 (1H, s) 5 Cp Cl O (CH ₂ ) ₂ OMe SO2 Me 81.4-82.6 ° C 6 Pr and O (CH ₂ ) ₂ OMe SO2 Me 84.2-86.2OC 7 Me Cl O (CH ₂ ) ₂ OMe SO ₂ Me 107.2-107.8OC 8 Cp br O (CH ₂ ) ₂ OMe SMe 94.4-94.8OC 10 Cp SO ₂ Me O (CH ₂ ) ₂ OMe br 104.2-105.2OC 11 Cp SMe O (CH ₂ ) ₂ OMe H 59-62 ° C

In the above table, C p represents a cyclopropyl group.

Example 2

To a solution of 5-cypropyl 1-4- (2-bromo-3- (2-methoxyethoxy) -412 methylsulphenylbenzoyl) isoxazole (1.9 g) in dichloromethane was added 3-chloroperoxybenzoic acid while maintaining the temperature around -15 ° C. The mixture was stirred at -15 ° C for one hour and then at ambient temperature again for one hour. The solution was then diluted with dichloromethane and washed with 2M sodium bisulfite solution and then water. The organic layer was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to dryness. The residue was purified by anhydrous column flash chromatography using a 1: 5 mixture of ethyl acetate and cyclohexane to give 5-cyclopropyl-4 (2-bromo-3- (2-methoxyethoxy) -4-methylsulfinylbenzoyl) from the appropriate eluate. isoxazole (compound 9) as a white solid.

Yield: 1.52 g, mp: 86.2-87.0 ° C.

Using the analogous procedure, the following compounds were prepared:

5-cyclopropyl-4- (2-methylsulfinyl-3- (2-methoxyethoxy)) benzoyl isoxazole (compound 12), m.p.

5-Cyclopropyl-4- (2-methylsulfonyl-3- (2-methoxyethoxy) (benzoylisoxazole) (compound 13), m.p. 111-114 ° C).

Reference example 1

A mixture of 3-cyclopropyl-1- (2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylphenyl) propane-1,3-dione (7.5 g) triethylorthoformate (10.3 g) in acetic anhydride was stirred with stirring Heat to reflux for 3 hours. The mixture was evaporated to dryness and the residue was treated with xylene and re-evaporated to give crude 3-cyclopropyl-1- (2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylphenyl) -2-ethoxymethylenepropane-1,3- Dione (8.5 g) as a dark brown oil which was no longer purified.

Using analogous methods, the following compounds are prepared (but not purified) from the corresponding substituted starting materials.

R R ² R ² R ⁴ Cp br O (CH ₂ ) ₂ OMe br 1-Me-Cp br O (CH ₂ ) ₂ OMe SO ₂ Me Me br O (CH ₂ ) ₂ OMe SO ₂ Me Cp C1 O (CH ₂ ) ₂ OMe SO ₂ Me Pr C1 O (CH ₂ ) ₂ OMe SO ₂ Me Cp br O (CH ₂ ) ₂ OMe SMe Cp SO ₂ Me O (CH ₂ ) ₂ OMe br Cp SMe ^: O (CH ₂ ) ₂ OMe H

In the above table, Cp is cyclopropyl.

reference example 2

A mixture of crude tert-butyl 2- (2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -3-cyclopropyl-3-oxopropanoate (10.2 g) and

F i i

i ŕ

- 14

1-4-Toluenesulfonic acid (2 g) in anhydrous toluene is stirred and refluxed for 2 hours. The cooled mixture was then washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness to give 3-cyclopropyl-1- (2-bromo-3- (methoxy ethoxy) -4-methylsulfonylphenyl) propane-1,3-dione as a brown oil.

Yield: 7.5 g, Bpectrum.

(CDCl) 0.9 (4H, m), 1.5 (1H, m), 3.1 (3H, s), 3.3 (3H, s), 3.6 (2H, t), 4.2 (2H t, 5.7 (1H, s), 7.15 (1H, d), 7.8 (1H, d).

Using an analogous procedure, the compounds listed in the following table are prepared from the corresponding substituted starting materials.

R ² Ο Ο

R ¹ R ² R ³ R ⁴ NMR Cp br O (CH ₂ ) ₂ OMe br 1.5 (4H, m) 2.1 (1H, m) 3.9 (3H, s) 4.2 (2H, t); 4.6 (2H, t); 6.3 (1H, s) 7.4 (1 H, d) 7.9 (1 H, d) 1-Me-Cp br O (CH ₂ ) ₂ OMe SO ₂ Me 1.2 (2H, m) 1.5 (2H, m) 1.7 (3H, s) 3.6 (3H, s) 3.8 (3H, s) 4.15 (2H, t) 4.7 (2H, t) 6.2 (1H, s) 7.65 ( 1H, d) 8.3 (1H, d) Me br O (CH ₂ ) ₂ OMe SO ₂ Me 2.4 (3H, s) 3.5 (3H, s) 3.7 (3H, s) 4.0 (2H, t) 4.6 (2H, t) 6.1 (1H, s) 7.55 (1H, d) 8.15 (1H, d) Cp C1 O (CH ₂ ) ₂ OMe SO ₂ Me 1.1 (4H, m) 1.7 (1H, m) 3.3 (3H, s) 3.5 (3H, s) 3.8 (2 H, t) 4.3 (2 H, t) 5.9 (1H, d) 7.3 (1H, d) 7.7 (1H, d) Pr C1 O (CH ₂ ) ₂ OMe SO ₂ Me 1.1 (6H, d) 2.4 (1H, m) 3.1 (3H, s) 33 (3H, s); 3.6 (2H, t); 4.2 (2H, t) 5.7 (1H, d) 7.1 (1H, d) 7.7 (1H, d) Me C1 O (CH ₂ ) ₂ OMe SC ^ Me 2.4 (3H, s) 3.5 (3H, s) 3.7 (3H, s) 4.0 (2H, t) 4.6 (2H, t) 6.0 (1H, s) 7.4 (1H, d) Cp br O (CH ₂ ) ₂ OMe f SMe 1.2 (4H, m) 1.8 (1H, m) 23 (3H, s) 3.5 (3H, s) 3.8 (2 H, t) 4.2 (2 H, t) 6.0 (1 H, s) 7.1 (2 H, m) Cp SC ^ Me O (CH ₂ ) ₂ OMe br 1.0 (4H, m) 2.0 (1H, m) 3.3 (3H, s) 3.5 (3H, s) 3.9 (2 H, t) 4.4 (2 H, t) 5.75 (1H, d) 7.0 (1H, d) 7.7 (1H, d) Cp SMe O (CH ₂ ) ₂ OMe H -

In the above table, Cp represents a cyclopropyl group.

Reference example 3

To a stirred mixture of tert-butyl-3-cyclopropyl-3-oxopropionate (4.5 g) and magnesium (0.68 g) in methanol was added tert-chloromethane, causing a violent reaction. The reaction mixture was then stirred for 0.25 hours and then evaporated to dryness. The residue was dissolved in acetonitrile and a solution was added

2-Bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl chloride in acetonitrile (50 mL) and the resulting mixture was stirred at ambient temperature for two hours and then allowed to stand overnight. The acetonitrile was removed under reduced pressure and the residue 6a was suspended in toluene. The toluene suspension was washed with 2M hydrochloric acid and then with water. The obtained organic solution was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to dryness to give crude tert-butyl 2- [2-bromo-3- (methoxyethoxy) -4-methylsulfonylbenzoyl] -3-cyclopropyl-3-oxopropionate as a crude brown oil. Yield: 10.27 g.

The compounds shown in the following table are prepared in an analogous manner.

R ² 0 0 R ³ X i i, 1 y ^{Zx of R;} R ⁴ / 1 C02tBu

R1 R ² ' R3 R ⁴ solvent Cp br O (CH ₂ ) ₂ OMe br CH3CN 1-Me-Cp br O (CH ₂ ) ₂ OMe SC ^ Me toluene Me br O (CH ₂ ) ₂ OMe SC ^ Me toluene Cp C1 O (CH ₂ ) ₂ OMe SO ₂ Me CH3CN Pr Cl O (CH ₂ ) ₂ OMe SC ^ Me CH3CN Me C1 O (CH ₂ ) ₂ OMe SC ^ Me CH3CN ^C P br O (CH ₂ ) ₂ OMe SMe CH3CN Cp SC ^ Me O (CH ₂ ) ₂ OMe br CH3CN Cp SMe O (CH ₂ ) ₂ OMe H · CH3CN

Benzoyl chlorides were prepared by refluxing the appropriate substituted benzoic acids for 3 hours.

Reference example 4

To a solution of potassium hydroxide (9.1 g) in water (25 mL) and denatured CH 3 OH (300 mL) was added ethyl 2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoate (24.3 g) . The resulting mixture was then heated at reflux for 4 hours and then allowed to cool overnight at ambient temperature. The reaction mixture was evaporated and the residue was dissolved in water and washed with ether. The aqueous layer was acidified to pH 1 with 2M hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness to give 2-bromo-3- (2-methoxyethoxy) -4-methylsulfenylbenzoic acid as a white solid. Yield: 19.4 g, nuclear magnetic resonance spectrum:

(CDCl3) 2.2 (3H, s),

3.25 (3H, s);

3.6 (2H, t);

3.8 (2H, t); 7.0 (2H, m).

Using an analogous procedure, 4-bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoic acid was prepared from ethyl 4-bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoate as a white solid.

Melting point: 156-157, S ° C.

Reference example 5

Ethyl 4-bromo-3- (2-methoxyethoxy) -2-methylsulfenylbenzoate (5.0 g) was stirred in acetic acid (8.0 mL) and acetic anhydride (2.0 mL) at 0 = * C . Hydrogen peroxide (11 mL) was added to the mixture. The resulting mixture was then stirred at 0 ° C for one hour and then at room temperature overnight. The mixture was then heated at 85 ° C for one hour. After cooling to ambient temperature, the mixture was diluted with ethyl acetate and washed with water, then with ferric sulfate and finally with water. The organic extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to dryness leaving 4-bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoate.

Yield: 4.7 g, nuclear magnetic resonance spectrum:

(CDCl 3) 1.8 (3H, t),

3.4 (3H, s);

3.8 (3H, s), 4.15 (2H, t), 4.3 (2H, q), 4.6 (2H, t), 7.15 (H, d), 7.85 ( H, d).

Reference example 6

Ethyl 2,4-dibromo-3- (2-methoxyethoxy) benzoate (32.2 g) was stirred in dimethylformamide (80 mL) with potassium carbonate (36 g). A solution of methanethiol (13 mL) in dimethylformamide (20 mL) was added to the obtained suspension. The resulting mixture was stirred overnight at ambient temperature. It was then diluted with ether and the mixture was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness. The residue was purified by silica gel column chromatography using a 1:20 mixture of ethyl acetate and cyclohexane to give 4-bromo-3- (2-methoxyethoxy) -2-methylsulphenylbenzoate as an oil which was not obtained from the appropriate eluate fraction. further characterized.

Yield: 3.5 g.

9 '

Reference example 7

To a 3M hydrochloric acid solution (700 mL) at 90 ° C was added 2- [3- (2-methoxyethoxy) -2-methylsulfenylphenyl] -4,4-dimethyl-2-oxazoline (48.7 g). ). The resulting mixture aa was stirred at 90 ° C for 3 hours and then cooled to ambient temperature a ^; extract with ethyl acetate. The organic extract was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness to give 3- (2-methoxyethoxy) -2-methylsulfenylbenzoic acid as a golden oil. Yield: 40.9 g, nuclear magnetic resonance spectrum:

(CDCl3) 2.5 (3H, s),

3.5 (3H, s);

3.8 (2H, m),

4.3 (2H, t);

7.1 (1H, m), 7.4 (1H, m), 7.6 (1H, m).

Reference example 8

A solution of 2- [3- (2-methoxyethoxy) phenyl] -4,4-dimethyl-2-oxazoline (63.4 g) in tetrahydrofuran was cooled to -40 ° C under an inert atmosphere. To this solution was then added n-butyllithium (122 mL 2.5M). The resulting mixture was stirred at -15 ° C for one hour and then recooled to -40 ° C. Dimethyldisulide (52.7 g) was added and the reaction mixture was allowed to warm to ambient temperature and stirred for one hour. Saturated ammonium chloride solution was added and the mixture was extracted with ether. The organic extract was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness and the residue was recrystallized from hexane to give 2- [3- (2-methoxyethoxy) -2-methylsulfenyl] phenyl] -4,4-dimethyl-2-oxazoline as a powder.

Yield: 56.5 g, m.p. 44.4-46.4 ° C.

»

Reference example 9

N- (2-Hydroxy-1,1-dimethylethyl) -3- (2-methoxyethoxy) -benzamide was stirred at 0 ° C. Thionyl chloride (90 mL) was then added over 1 hour. The resulting solution of Ba was stirred at 15 ° C for an additional hour and 30 minutes while diethyl ether was added. The residual solvents are removed in vacuo and the residue is suspended in diethyl ether, washed with 2M sodium hydroxide and the organic phase is separated. The organic extract was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was evaporated to dryness and the residue distilled under reduced pressure to give 2- [3- (2-methoxyethoxy) phenyl] -4,4-dimethyl-2-oxazoline.

Yield: 66 g, melting point: 164-168 ° C at 200 Pa.

Reference example 10

2-Amino-2-methylpropan-1-ol (57.6 g) was dissolved in dichloromethane and cooled to 0 ° C. A solution of 3- (2-methoxyethoxy) benzoyl chloride (67.8 g) in dichloromethane was added and the solution was stirred overnight at ambient temperature, during which time a precipitate formed. The mixture was filtered and the filtrate was evaporated to dryness to give N- (2-hydroxy-1,1-dimethylethyl) -3- (2-methoxyethoxy) benzamide as a syrup.

Yield: 95.5 g, nuclear magnetic resonance spectrum:

(CDCl3) 1.4 (6H, s),

3.5 (3H, s);

3.65 (2 H, s),

3.7 (2H, t), 4.2 (2H, t), 5.4 (1H, s), 6.3 (1H, b), 7.0 (1H, m), 7.3 (2H) , m).

Reference example 11

3- (2-Methoxyethoxy) benzoic acid (72.9 g) and tiotyl chloride (119 <3) were heated together at reflux for 1.5 hours and then allowed to cool overnight. The thionyl chloride was evaporated under reduced pressure. The residue was distilled under reduced pressure to obtain

3- (2-methoxyethoxy) benzoyl chloride.

Yield: 67.7 g.

boiling point: 130 ° C at 53.2 Pa.

Reference example 12

2-Methoxyethyl 3- (2-methoxyethoxy) benzoate (133 g) was dissolved in denatured CH 3 OH and 2M sodium hydroxide solution and the solution was heated at reflux for 1.5 hours. The mixture was then allowed to cool and ice was added. The resulting mixture was washed with ether, the aqueous layer was acidified to pH 1 with hydrochloric acid and filtered. The filter residue is washed with water and air-dried. The residue was recrystallized from ether and petroleum ether (m.p. 40-65 ° C) to give 3- (2-methoxyethoxy) benzoic acid in the form of a white solid.

Yield: 86 g, mp 79.6-81.8 ° C.

Reference example 13

3-Hydroxybenzoic acid (73 g) was dissolved in dimethylformamide and potassium carbonate (160 g), 2-chloroethyl methyl ether (200 g) and potassium iodide (8.8 g) were added. The mixture was then heated to 72 ° C for 42 hours. After cooling, the mixture is poured onto ice and extracted with ether. The organic extract is washed with 2M sodium hydroxide solution, water and brine, then dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to dryness to give 2-methoxyethoxy-3- (2-methoxyethoxy) benzoate which was no longer purified.

Yield: 135.5 g.

The present invention also provides a method of controlling weed growth (i.e., undesirable vegetation) at a given location. It consists in applying to said locus a herbicidally effective amount of at least one isoxazole derivative of the general formula I. For this purpose, the isoxazole derivatives according to the invention are used in the form of herbicidal compositions (ie in combination with compatible diluents or carriers and / or surfactants). suitable for use in herbicidal compositions.

The compounds of the formula I according to the invention exhibit herbicidal activity against dicotyledonous and monocotyledonous weeds (i.e. broadleaf weeds and grass weeds) in pre- and / or post-emergence application.

Pre-emergent application 'means application to the soil in which weed seeds or seedlings are present before they reach the soil level. Postemergence application means application to aerial or exposed parts of weeds after emergence above the soil surface.

For example, the compounds of formula I may be used to inhibit growth

- broadleaf weeds including Abutilon theophrasti, Amaranthus retroílexus, Bidens pilosa, Chenopodium album. Galium aparine, Ipomoea spp., Ipomoea purpurea, Sesbania exaltata, Sinapis arvensis, Solanum nigrum and Xanthium strumarium,

- grassy weeds such as, for example, Alopecurus myosuroides, Avena laua, Digitaria sanguinalis, Echinochloa crus-galli, Sorghum bicolor, Eleusine indica and Setaria spp., such as Setaria gaberia or Setaria viridis, and

- weed weeds, between. such as Cyperus esculentus.

The amount of compounds of general formula I applied varies depending on the nature of the weed to be suppressed, the composition used, the application time and the climatic and soil conditions as well as the nature of the crop;

when weed control is carried out on the area on which the crop is growing. In case the herbicidal ί

the active substance is applied to the land on which the usefulness grows

it is then necessary that its application rate is sufficient to effectively control weeds without causing substantial permanent damage to the crop. Taking into account these circumstances, generally an application rate of 0.01 to 5 kg of active ingredient per hectare of treated soil gives good results. It will be understood, however, that application rates may;

be higher or lower, depending on the specific conditions of each case of plant growth suppression solved.

The compounds of formula (I) may be used to selectively inhibit weed growth, for example, to control the growth of those weed species already mentioned above, or by postemergence application, in a directed or non-directional manner, e.g. on the area used or intended for the cultivation of crops such as cereals, in particular wheat, barley, oats, maize and rice, soya, field and radish, peas, lanterns, cotton, peanuts, flax, onions, carrots, cabbages, oilseed, rape, sunflower, sugar beet, or permanent or sown pasture, before or after sowing of the crop. Application rates of 0.01 to 4.0 kg, preferably 0.01 to 4.0 kg, are particularly suitable for the selective control of weed growth in a locus infested with weeds which are used or intended for the cultivation of useful crops, for example of the aforementioned crop plants. 2 kg of active substance per hectare of treated area.

The compounds of the formula I can also be used for controlling weed growth, in particular of the abovementioned weeds, by pre- or post-emergence application in orchards or other areas with tree stands, for example in forests, woodlands, parks, palm tree plantations and rubber plantations. For this purpose, a directed or non-directed application (for example, directed or non-directed spraying) to weeds or to soil in which weed and rto growth is expected to occur before or after planting trees or plants at application rates of 0.25 to 5 kg may be used. preferably 0.5 to 4 kg of active ingredient per hectare of treated area.

The compounds of formula I are:. they may also be used to suppress weed growth, in particular those weeds already mentioned above, in sites which are not areas of crop production but where weed growth is nevertheless undesirable.

Examples of such sites that are not crops are airports, factory lands. Railway embankments, river banks, irrigation and other waterways, shrubs, ice-laying and uncultivated land. This is particularly the case when weed growth is suppressed in order to reduce the risk of fires. When active agents are used for this purpose, where a total herbicidal effect is often required, these active agents are normally applied at doses higher than those used in crop areas. The exact application in these cases depends on the nature of the vegetation whose growth is to be suppressed and the desired degree of herbicidal action.

Particularly suitable for this purpose is pre- or post-emergence application in a directional or non-directional manner (e.g., directional or non-directional spraying) at application rates of 1 to 20 kg, preferably 5 to 10 kg, of active compound per hectare of area treated.

When used to suppress weed growth by pre-emergence application, the compounds of Formula I may be incorporated into the soil in which weed growth is expected. It should be noted. That is, when the compounds of formula I are used to suppress weed growth by post-emergence application, i. by application to airborne or exposed portions of the resulting weeds, the compounds of formula (I) also come into contact with the soil and may at the same time act preemergence to the later germinated weeds in the soil.

If long-term weed growth control is desired, the application of the compounds of formula I may optionally be repeated.

The present invention also provides a non-pesticidal composition comprising one or more isoxazole derivatives of Formula I in combination with one or more compatible.

for herbicidal application, acceptable diluents or carriers and / or surfactants, wherein the 2-cyano-2,3-

the dione derivative or salt thereof is preferably dispersed homogeneously in said diluents or carriers / below compatible, herbicidal acceptable diluents or carriers herein are understood as diluents and carriers that are acceptable as suitable for the preparation of herbicidal compositions and which are compatible with compounds of the formula I: the same applies to surfactants. The term homogeneously dispersed includes compositions in which the compounds of formula I are dissolved in the other ingredients. The term herbicidal composition is used herein in a broad sense and includes not only compositions that are already ready for use as herbicides, but also concentrates that need to be diluted before ingestion. These compositions preferably contain 0.05 to 90% by weight of one or more compounds of formula (I).

The herbicidal compositions may contain both a diluent or carrier, as well as a surfactant (e.g. wetting, dispersing or emulsifying). The surfactants which may be present in the herbicidal compositions may be of the ionic or non-ionic type, such as sulforicinoleate, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyarylphenols, for example nonyl or octylphenols, or carboxylic esters. acids derived from anhydride sorbitols which are soluble due to the etherification of free hydroxyl groups by condensation with ethylene oxide, alkali metal and alkaline earth metal salts of sulfuric acid and sulfonic acid esters such as dinonyl and dioctyltinium sulfosuccinates and alkali metal and alkaline earth metal salts of high molecular weight for example, sodium and potassium lignosulfonate and sodium and calcium alkylbenzenesulfonate.

A suitable amount of surfactant in the herbicidal composition of the invention is up to 10% by weight, for example 0.05 to 10% by weight, but the herbicidal compositions of the invention may also contain higher amounts of surfactant, for example up to 15% by weight in the case of liquid emulsifiable suspension concentrates and up to 25% by weight in the case of liquid water-soluble concentrates.

Examples of suitable solid diluents or carriers are, for example, aluminum silicate, talc, calcined magnesium, diatomaceous earth, calcium phosphate, cork, absorbent carbon black, and clays such as kaolin or bentonite. Solid compositions (which may be in the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula I with solid diluents or impregnating solid diluents or carriers with solutions of the compounds of formula I in volatile solvents, evaporating solvents and optionally grinding the product to obtain a powder. . Granular films can be prepared by absorbing the compounds of formula I (dissolved in suitable solvents, which may optionally be volatile) to solid diluents or carriers in granular form and optionally evaporating the solvents, or granulating the compositions in powder form obtained as described above. Solid herbicidal compositions, in particular wettable powders and granular compositions, may contain a wetting or dispersing agent (for example of the type already described) which, if solid, may also serve as a diluent or carrier.

Liquid compositions of the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions, which may contain a surfactant. Suitable liquid diluents for incorporation into the liquid compositions are water, glycols, tetrahydrofurfuryl alcohol, acetoenenone, cyclohexanone, isoorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic oil fractions (and mixtures of these diluents). The surfactants which may be present in the liquid compositions may be new or non-ionic surfactants (for example of the type described above) and, when liquid, may also serve as a diluent or carrier.

Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, in particular in the case of liquid concentrates in which the oil is a diluent or carrier, thereby obtaining ready-to-use compositions. .

If desired, liquid compositions containing a compound of formula (I) may be used in the form of self-emulsifying concentrates containing the active ingredients dissolved in emulsifying agents or solvents containing emulsifying agents which are compatible with the active ingredients, by simply adding water to such concentrates to obtain ready-to-use compositions. .

Liquid concentrates in which the diluent or carrier is oil can be used without further dilution using an electrostatic spray technique.

I.

Íí .ί

The herbicidal compositions according to the invention may, if necessary, also contain conventional additives such as adhesives, protective colloids, thickeners, penetrating agents;

stabilizers, sequestering agents, antisedimenting agents, coloring agents and corrosion inhibitors. These additives may also serve as carriers or diluents.

Unless expressly stated otherwise, all percentages are:

not the contents given in the following part of the description by weight.

and

Preferred herbicidal compositions of the invention are:

i!

aqueous suspension concentrates containing 10 to 70%;

one or more compounds of the formula I, 1 to 10% of a surfactant, 0.1 to 5% of a thickener and 15 to 87.9% of water,

- wettable powders containing 10 to 90% of one or more compounds of the formula I, 2 to 10% of a surfactant and 8 to 88% of a solid diluent or carrier,

- soluble powders containing 10 to 90% of one or more compounds of the formula I, 2 to% sodium carbonate and 0 to 88% of a diluent diluent,

liquid water-soluble concentrates containing up to 50%, for example 10 to 30%, of one or more compounds of the formula I, 5 to 25% of a surfactant and 25 to 90%, for example 45 to 85% of a water-miscible solvent, and water

- liquid emulsifiable suspension concentrates containing 10 to 70% of one or more compounds of the formula I, 5 to 15% of a surfactant, 0.1 to 5% of a thickener and 10 to 84.9% of an organic solvent,

granular compositions containing 1 to 90%, for example 2 to 10% of one or more compounds of the formula I, 0.5 to 7%, for example 0.5 to% of surfactant and 3 to 98.5%, for example 88 to 97.5% granular carrier, and

emulsifiable concentrates containing 0.05 to%, preferably 1 to 60%, of one or more compounds of the formula I, 0.01 to 10%, preferably 1 to 10% of a surfactant and 9.99 to 99.94 %, Preferably 39 to 98.99% organic solvent.

The herbicidal compositions of the invention may also contain the compounds of formula I, in combination, preferably in homogeneously dispersed form, with one or more pesticidal or herbicidally active compounds and optionally one or more compatible pesticidally and herbicidally acceptable diluents or carriers. , surfactants and conventional additives as described above.

Examples of other pesticidal or herbicidally active compounds that may be included (or used together) in the herbicidal compositions include

- in order to broaden the spectrum of suppressed weed species, for example, herbicides: · alachlor, i. 2-chloro-2,6-diethyl-N- (methoxymethyl) acetanilide, atrazine, i. 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, bromoxynil, i. 3,5-dibromo-4-hydroxybenzonitrile, chlorotoluron, i.e., N '- (3-chloro-4-methylphenyl) -N, N-dimethylurea, cyanazine, i. 2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine,

2,4-D, i.e. 2,4-dichlorophenoxyacetic acid, dicamba; 3,6-dichloro-2-methoxybenzoic acid, difenzoquat, i.e. 1,2,2-dimethyl-3,5-dienylpyrazolium salt, flampropmethyl, e.g. methyl N-2- (N-benzoyl-3-chloro-4-fluoro-anilino) propionate, fluometuron, i. N- (3-trifluoromethylphenyl) -N, N-dimethylmorea, isoproturon, i. N- (4-isopropylphenyl) -N, N-dimethylurea,

insecticides, for example synthetic pyrethroids, for example peimethrin and cypermethrin, and

fungicides, for example carbamates such as methyl N- (1-butylcarbamoylbenzimidazol-2-yl) carbamate, and triazoles, for example 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazole-1- y1) -2-butanone.

The pesticidal active compounds and other biologically active substances which may be included (or used together) in the herbicidal compositions of the invention, exemplified above and which are acids, may optionally be used in the form of conventional derivatives such as alkali metal salts, amine-derived salts and esters.

The present invention also provides an article of manufacture comprising at least one of the isoxazole derivatives of the formula I, or preferably the herbicidal composition described above, and preferably the herbicidal concentrate, which must be diluted before use, comprising at least one of the isoxazole derivatives of the formula I a derivative (s) of formula (I) or said herbicidal composition and instructions physically associated with the aforementioned reservoir. The container is a container which is conventionally used for the storage of chemical substances which are solid at ambient temperature and of herbicidal compositions, in particular in the form of concentrates, for example a metal sheet can, which may be covered with a lacquer layer or plastics inside. , or glass or plastic bottles. In the case where the content of the container is in the solid state and is, for example, a granular herbicidal composition, the container may consist of a box of, for example, cardboard, plastic or metal sheet, or a bag.

Suitable containers will have sufficient content for an amount of an isoxazole derivative or herbicidal composition sufficient to treat at least 40 acres of the plot carried out to inhibit weed growth on the plot, the container content not exceeding a size that is still suitable for acceptable handling of the container. The instructions will be physically associated with the cartridge and can be directly printed on a label that is affixed to the cartridge. The instructions will provide information on the content of the container and that, if appropriate, the content of the container should be used to control weed growth at application rates of 0.01 to 20 kg of active ingredient per hectare of area to be treated as described.

$

WITH.

The following examples illustrate the herbicidal compositions of the invention.

Example C1

From the following components:

active substance (compound 1)

33% (w / v) potassium hydroxide solution tetrahydrofurfuryl alcohol% w / v

% w / v

% w / w

water to 100% v / v, a soluble concentrate is formed, with a stirred mixture of tetrahydrofurfuryl alcohol, the active compound (compound 1) and 90% v / v. of the total amount of water, slowly add the potassium hydroxide solution until a stable pH of 7 to 8 is reached and then the volume of the concentrate is topped up with the remaining amount of water.

Similar soluble concentrates can be prepared by replacing said isoxazole (compound 1) with other compounds of formula I.

Example C.

From the following components:

active ingredient (Compound 1) sodium dodecylbenzenesulfonate

Sodium 1ignosulfonate sodium formaldehyde alkylnaphthalenesulfonate microfine silica kaolin

% w / v

% w / w

% w / w

% wt. / hm.

Ss hm. / hm.

% w / w, a wettable powder is prepared by mixing all of the above ingredients together and grinding the resulting mixture in an air jet metal mill.

Similar wettable powders can be prepared by replacing said isoxazole (compound 1) with other compounds of formula 1.

Example C3

From the following components:

active ingredient (Compound 1)% w / w

sodium dodecylbenzenesulphonate microfine silica sodium bicarbonate% wt. / hm.

% wt. / hm.

A water-soluble powder is prepared by mixing and co-milling in a hammer mill.

Similar water-soluble powders can be prepared by replacing said isoxazole (compound 1) with other compounds of formula I.

Representative compounds of the general formula were used in the following herbicidal applications

I, according to the invention

A method of using herbicidal compounds

(a) General methodology

Appropriate amounts of compound compounds used to treat plants were dissolved in acetone to give solutions equivalent to application rates of up to 4000 g test compound per hectare (g / ha). These solutions were applied using a standard laboratory sprayer releasing 290 liters of spray liquid per hectare.

b) Suppressing weed growth by pre-emergence application

The seeds were sown in 70 mm square plastic 75 mm depth cores into non-sterile soil. The following seed quantities were used per root:

Weed type Approximate number of seeds / root

1) Broadleaf weeds Abutilon theophrasti 10 Amaranthus retroflexus 20 Gallium aparine 10 Ipomoea purpurea 10 Sinapis arvensis 15 Xanthium strumarium 2 2) grass weeds Alopecurus myosuroides 15 Avena fatua 10 Echinochloa crus-galli 15 Setaria viridis 20 3) šáchorovité weeds Cyperus esculentus 3

Crops

1) broadleaf cotton soybean crops

2) grassy crops maize rice wheat

6th

The compound of the invention is applied to the surface of the soil containing said seeds as described in a) above. For each crop and for each weed, there is one rooted, which is not sprayed at all and one rooster, which is exposed to the spraying with acetone alone.

After the spraying, the roots are placed in a greenhouse on a capillary mattress where they are treated with top irrigation. 20 to 24 days after spraying, a visual assessment of damaged crop plants is performed. The results shall be expressed as a percentage reduction in growth or damage to crop plants or weeds as compared to the plant status in the control roots.

c) Weed control of weeds by postmenemenent application

Weeds and crops are sown directly into a rooting compost (John Innes) filled into 70 mm square and 75 mm deep crustaceans except Amarnthus, which is planted at the seedling stage and transferred to the roots until one week after spraying. The plants are then grown in the greenhouse until ready for spraying with the plant treatment compounds. The following numbers of plants in roots are used in this application.

Plant species Number of plants / Growth stage

1) broadleaf weeds

Abutilon theophrasti 3 First until Second sheet Amaranthus retroflexus 4 First until Second sheet Gal1ium aparine 3 First whorl Ipomoea purpurea 3 1, until Second sheet sinapis arvensis 4 Second sheet Xanthium i strumarium 1 Second until Third sheet

2) grass weeds

Alopecurus myosuroides 8-12 1. until Second sheet Avena íatua 12-18 1. until Second sheet Echinochloa crus-galli 4 First until Second 1 sure Setaria viridis 15-25 First until Second sheet

3) weed weeds

Cyperus esculentus 3 Third sheet 4) broad-leaved crops cotton 2 First sheet soy 2 Second sheet 5) grassy crops sweet corn 2 Second to 3rd sheet rice 4 Second up to 3 sheets wheat 5 Second up to 3 sheets.

The compounds used to treat the plants are applied to the plants as described in a). For each crop and weed there is a single crusher that is not sprayed at all, and a crusher that is exposed only to the spray of acetone alone.

After spraying, the crushers are placed in a greenhouse on a capillary mattress, where they are exposed to the top irrigation even after 24 hours and then further moistened with a regulated underwater irrigation. 20-24 days after spraying, a visual assessment of crop damage and weed growth suppression is performed.

The results obtained are expressed as a percentage reduction of the plants or damage to crops or weeds in comparison with the plant status in the control roots.

r

The compounds of the invention exhibited an excellent level of herbicidal activity against weeds used in the above-mentioned!

tests and at the same time showed good tolerance from the crops. i

and

When compounds 1 to 35 are applied pre- or post-gently at a rate of 1000 g / ha, they achieve a% reduction in growth of one or more weed species.

Claims (10)

A 4-benzoylisoxazole derivative of the general formula I in which: F: ¹ (I) means a straight or branched alkyl group having 1 to 4 carbon atoms or a 3- or 4-membered cycloalkyl group optionally substituted by a straight or branched alkyl group containing up to 4 carbon atoms. represents a halogen atom or a group selected from the group -O (CH 2) -OR ⁵ , -CO ₂ R ^5, and nitro. represents a halogen atom or a group selected from the group consisting of R ⁵ , -OR ⁵ , -S (O) mR ⁵ and -O (CH 2), -OR ⁵ , represents a hydrogen atom or a halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) _m R ⁵ , -O (CH 2) -t-OR ⁵ and a nitro group, with the proviso that at least one of R ² , R ³ , and R ⁴ is -O ( CH 2) < _(- OR ⁵ , R ⁵ denotes a straight or branched alkyl group, containing y _; r: T -l II having 1 to 4 carbon atoms, which is optionally substituted by one or more halogen atoms, m represents zero, 1 or 2a g represents an integer from 1 to 3. A compound according to claim 1, wherein R ³ is -O- (CH 2) n -OR 5. A compound according to claim 1 or 2, wherein: R 2 is a hydrogen atom or a group selected from the group consisting of R ^5, -OR ^5, -S (O) _m R ⁵ ·, -CO2 ^R5 and nitro; R ³ represents the group -O (0 ') - OR ⁵ , R * represents a hydrogen atom or a halogen atom or a group selected from the group consisting of R ⁵ , -OR ⁵ , <-S (O) _m R ^5, and nitro, and q is 2 or 3. A compound according to claim 1, 2 or 3 having one or more of the following features: ri R 2 R4 R ⁵ represents a methyl group, an ethyl group, a 1-methylethyl group, a cyclopropyl group or a 1-methylcyclopropyl group. is chlorine, bromine or fluorine or a group selected from the group consisting of R ^5, and -S (0) m R ⁵ is chlorine, bromine or fluorine atom or a group selected from the group consisting of R ^5, and -S (0) m R ⁵ represents a straight or branched alkyl group having 1 to 4 carbon atoms, which is optionally substituted by one or more halogen atoms. A compound according to any one of the preceding claims having one or more of the following features: R ¹ represents 1-methylethyl, 1-methylcyclopropyl III »ί I r or a cyclopropyl group, i R 5 represents a methyl group, an ethyl group, or a tri -? íluórmetylovú group, at least one of R ² and R ⁴ is - S (0) m CH3 a. 'Provided that R ² and R ⁴ are not simultaneously a group -SO2 CH3, q is 2. A compound according to any one of the preceding claims wherein R 1 represents a cyclopropyl group, R2 represents a chlorine atom, a bromine atom or a fluorine atom or a group selected from methyl, trifluoromethyl and -S (O) mCHa, R3 is -O (CH2) "- 0R ⁵ / R ⁴ represents a chlorine atom, a bromine atom or a fluorine atom or a group selected from methyl, trifluoromethyl and -S (O) _m CH 3, at least one of R ² and R ⁴ being -S (O) mCH 3 provided that: R ² and R ^{4 are} not -SO 2 CH 3 and q is 2. The compound of claim 1 or 2, which is a compound selected from the group consisting of: 4- / 2,4-dibromo-3- (2-methoxyethoxy) benzoyl-5-cyclopropylisoxazole,. · 4/2-bromo-3- (2-methoxyethoxy) -4-methylsulfonyl-benzoyl / -5cyklopropylizoxazol, 4/2-bromo-3- (2-methoxyethoxy) -4-methylsulfonyl-benzoyl / -5 (1-methylcyclopropyl) isoxazole. 4/2-bromo-3- (2-methoxyethoxy) -4-metylsulfonylbenzoy1 / methylisoxazole. 4- (2-chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) -5-cyclopropylisoxazole, 4/2-chloro-3- (2-methoxyethoxy) -4-metylsulíonylbenzoy1 / -5izopropylizoxazol, 4/2-Chiou-3- (2-methoxyethoxy) -4-metylsulfonylbenzoy1 / 5- IV cyclopropylisoxazole, 4- [2-Bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] -5-cyclopropylisoxazole, 4/4-bromo-3- (2-methoxyethoxy) -2-metylsulfony1benzoy1 / -5H Ir cyclopropylisoxazole, 5-cyklopropy1-4- / 2-metylsulfény1-3- (2-metcxyetoxy) benzoy1 / isoxazole, 5-cyclopropyl-4- (2-methylsulfinyl-3- (2-methoxyethoxy) benzoyl) isoxazole; and 5-cyklopropy1-4- / 2-metylsulfony1-3- (2-methoxyethoxy) benzoy1 / isoxazole. Third A process for the preparation of a compound of formula (I), wherein R ^{1 of} claim 1, of formula (II) R ³ and R ⁴ are as defined in claim 1 and is a leaving group, with a nydroxylamine salt, by reacting a compound of formula III (III) wherein R 1 is as defined in claim 1 with a compound of formula IV (IV) wherein R 3 ² , R ³ and R ⁴ are as defined in claim 1, and reacting a compound of formula V (V) wherein R ¹ is as defined in claim 1 and Z is a carboxyl group or a reactive derivative thereof, or a cyano group, with an appropriate an organometallic reagent. A composition according to any one of claims 1 to 7 in combination with an agriculturally acceptable diluent or carrier and / or a surfactant. 10. A method of controlling weed growth in a locus, comprising applying to said locus a herbicidally effective amount of a 4-benzoylisoxazole derivative of the formula I as claimed in any one of claims 1 to 7. The method of claim 10, wherein said site is an area that is used or intended to grow crops, said compound being applied at an application rate of 0.01 to 4.0 kg per hectare.