SI9300061A - 4-benzoylisoxazole derivatives and their use as 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

(54) 4-BENZOYLISOXAZOLE DERIVATIVES USED AS HERBICIDES

Fig. 9300061 (57) 4-Benzoylisoxazole derivatives of general

in which R ¹ represents an alkyl group or an optionally substituted cycloalkyl group; R ² represents a halogen atom selected from R ⁵ , -OR ⁵ , -S (O) _m R ⁵ '

-O (CH ₂ ) _q -OR ⁵ , -CO 2) -R ⁵ and nitro. R ³ represents a halogen atom or a group selected from 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 selected from R ⁵ , -OR ⁵ , -S (O) m R ⁵ , -O (CH 2) q-OR ⁵ and nitro; provided that at least one of the groups R ² , R ³ and R ⁴ is -O (CH 2) q-OR ⁵ ; R ⁵ represents a straight or branched chain alkyl or alkoxy group containing up to four carbon atoms optionally substituted by one or more halogen atoms; m means zero, one or two; and q means even

4-BENZOYLISOXAZOLE DERIVATIVES USED AS HERBICIDES

The present invention relates to novel 4-benzoylisoxazole derivatives, compositions containing them and their use as herbicides. The herbicidally active 4-benzoylisoxazoles are described in European Patent Publication no. 0418175.

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

O _R 2

R ³

Ό 'Rl ^^^ r4 (I) in which

R represents a straight- or branched-chain alkyl or alkoxy group containing up to four carbon atoms, or a tri- or four-membered cycloalkyl group optionally substituted by a straight or branched chain containing up to four carbon atoms;

R ² represents a halogen atom, a group selected from R ⁵ , -OR ⁵ , -S (O) mR ⁵ , -O (CH 2) -OR ⁵ , -CO ₂ R ⁵ and nitro.

R ³ represents a halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) mR ⁵ and -O (CH 2) _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 (CH 2) _q -OR ⁵ and nitro;

provided that at least one of the groups R ² , R ³ and R ⁴ is -O (CH ₂ ) -OR ⁵ ;

R ⁵ represents a straight or branched chain alkyl or alkoxy group containing up to four carbon atoms optionally substituted by one or more halogen atoms;

m means zero, one or two; and q is an integer from one to three.

The compounds of the invention show unexpected and significant high herbicidal activity against important weed species, including rapeseed (Xanthium strumarum), compared to known compounds.

Preferred compounds of formula (I) are those wherein R is -O (CH ₂ ) _q -O R ⁵ .

The group of compounds of general formula (I) which are preferred by their herbicidal properties is one in which:

R ² represents a halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) mR ⁵ , -CO 2 r ⁵ and nitro;

R ³ is -O (CH ₂ ) g-OR ⁵ ;

R ⁴ represents a hydrogen or halogen atom or a group selected from R ⁵ , -OR ⁵ , -3 (O) ⁵ and nitro; and q means two or three.

The following group of compounds of general formula (I), which are preferred by their herbicidal properties, are those with one or more of the following characteristics:

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

R ⁴ represents a chlorine, bromine or fluorine atom, or a group selected from R ⁵ and -SiO ^ R ⁵ ;

R ⁵ represents a straight or branched chain alkyl or alkoxyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms.

The following group of compounds of general formula (I), which are advantageous for their herbicidal properties, are those with one or more of the following characteristics:

R represents a 1-methylethyl, 1-methylcyclopropyl or cyclopropyl group;

R ⁵ represents a methyl, ethyl or trifluoromethyl group, at least one of R ² and R ⁴ represents -S (O) _m CH ₃ , provided that R ² and R ⁴ do not simultaneously represent -SO ₂ CH ₃ ;

q means two.

In particular, because of herbicidal properties, a group of compounds of general formula (I) are preferred in which:

R ¹ represents a cyclopropyl group;

R represents a chlorine, bromine or fluorine atom, or a group selected from methyl, trifluoromethyl and -S (O) _m CH ₃ ;

R ³ is -O (CH _O ) '- O R ⁵ ;

R ⁴ represents a chlorine, bromine or fluorine atom, or a group selected from methyl, trifluoromethyl and -SiOl ^ R ⁵ ;

at least one of the groups R ² and R ⁴ is -S (O) mCH ₃ , provided that R ² and R ⁴ do not simultaneously represent -SO ₂ CH ₃ ; and q means two.

Due to their herbicidal action, the following compounds are particularly preferred:

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- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] 5-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-methylsulphenylbenzoyl) 5-cyclopropylisoxazole;

9. 4- [2-Bromo-3- (2-methoxyethoxy) -4-methylsulfinylbenzoyl) 5-cyclopropylisoxazole;

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

11. 5-cyclopropyl-4- [2-methylsulphenyl-3- (2-methoxyethoxy) benzoyl] isoxazole;

12. 5-cyclopropyl-4- [2-methylsulfinyl-3- (2-methoxyethoxy) benzoyl] isoxazole; and

13. 5-cyclopropyl-4- [2-methylsulfonyl-3- (2-methoxyethoxy) benzoyl] isoxazole.

Numbers 1 to 13 were assigned to these compounds for reference and identification hereinafter.

Compounds of general formula (I) can be prepared by using or adapting known methods (i.e., methods previously used or described in the literature), for example, such as those described in the following text.

In the following description, where the symbols appearing in the formulas are not specifically defined, it is to be understood that they are defined as in the text before according to the first definition of each symbol in the specification.

It should be understood that in the description of the following processes the sequences can be performed in different sequences and that suitable protecting groups may be needed to achieve the compounds sought.

Depending on the characteristic of the present invention, compounds of general formula (I) can be prepared by reaction of a compound of general formula (II):

R2 0 0 / L · V | T k where R ¹ , R ² , R ³ and R ⁴ as defined above, L a prominent group, s hydroxylamine salt. Usually

hydroxylamine hydrochloride is preferred. In general, L is alkoxy, for example ethoxy, or Ν, Ν-dialkylamino, for example dimethylamino. The reaction is usually carried out in a solvent such as ethanol or acetonitrile, optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate.

In view of the further characteristic of the compound of general formula (I), general formula (III):

of the present invention can be prepared by reaction of compound s

(ΠΓ) in which R ^{7 is} as defined above with a compound of general formula (IV):

wherein R ² , R ³ and R ^{4 are} as defined above. The reaction is usually carried out in the presence of a catalyst, which is a Lewis acid, such as aluminum chloride, at a temperature between room temperature and 100 ° C.

According to a further feature of the present invention, compounds of general formula (I) can be prepared by reaction of a compound of general formula (V):

Y

(V) 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 a suitable organometallic reagent such as Grignard's reagent, or some organolithium reagent. Usually the reaction is carried out in an inert solvent, such as ether or tetrahydrofuran, at a temperature of

0 ° C to the reflux temperature of the mixture.

Intermediates in the preparation of compounds of general formula (I) can be prepared by the use or adaptation of known methods.

Compounds of general formula (II) can be prepared by reaction of compounds of general formula (VI):

(VI) wherein R ¹ , R ² , R ³ and R ⁴ as hereinbefore defined are either trialkyl orthoformate such as triethyl orthoformate or dimethyltimimide dialkylacetal such as dimethylformamide dimethyl acetal. The reaction with triethyl orthoformate is usually carried out in the presence of acetic anhydride at the reflux temperature of the mixture, and the reaction with dimethylformamide dialkyl acetal is optionally in the presence of an inert solvent at room temperature to the reflux temperature of the mixture.

The reaction is generally carried out in the presence of an organic base such as triethylamine in an inert solvent, such as toluene or dichloromethane, at a temperature between -20 ° C and room temperature.

Compounds of general formula (VI) can be prepared by the reaction of acid chloride of formula (VII):

C0C1

"O, 49,, in which R, R and R as defined herein, with a metal salt of a compound of formula (VIII):

0 X Λ • R + ^^^ OtBu (VIII) in which R ^{1 is} as previously defined to give the compound of formula (IX):

(ix) wherein R ¹ , R ² , R ² and R ^{4 are} as previously defined, which is subsequently decarboxylated to give the compound of formula (VI). The reaction to produce the compound of formula (IX) is usually carried out in a solvent such as a lower alcohol, preferably methanol, in the presence of a metal, preferably magnesium. Decarboxylation is usually performed by refluxing a compound of formula (IX) in the presence of a catalyst such as paratoluenesulfonic acid in an inert solvent e.g. toluene.

The intermediates of general formula (III), (IV), (V), (VII) and (VIII) are known or can be prepared by the use or adaptation of known methods.

It will be appreciated by those skilled in the art that certain substances of general formula (I) can be prepared by interconversion of other substances of general formula (I), and such interconversions e further determine the features of the present invention. Examples of such interconversions are described later.

According to a further feature of the present invention, compounds may be prepared in which m is one or two by oxidizing the sulfur atom of compounds in which m is zero. Oxidation of the sulfur atom is usually carried out with, for example, 3-chloroperoxybenzoic acid in an inert solvent, such as dichloromethane, at a temperature of -40 ° C to room temperature.

The following examples illustrate the preparation of compounds of general formula (I), and the following reference examples illustrate the preparation of intermediates of the invention. in this specification boiling. means boiling point, soil. but the melting point. Where NMR letters appear, the characteristics of the proton nuclear magnetic resonance spectrum follow.

EXAMPLE 1

Mixtures of 3-cyclopropyl-2-ethoxymethylene-1- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylphenyl] propane 1,3 dione (8.5 g) and hydroxylamine hydrochloride (1.77 g) in ethanol sodium acetate (1.65 g) was added. The mixture was stirred at room temperature overnight and then evaporated to dryness. The residue was dissolved in ethyl acetate and washed with water, dried (anhydrous MgSO ₄ ) and filtered. The filtrate was evaporated to dryness. The residue was chromatographed on silica eluting with a mixture of ethyl acetate and cyclohexane (1: 5) to give 4- [2bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] -5-cyclopropylisoxazole (compound 2) as yellow oil (3.3 g), NMR (CDCl ₃ ), 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 ( lH, s).

The following compounds of general formula (I) were prepared in a similar manner from suitably substituted starting materials.

Sp j. no. R ¹ R ² R ³ R ⁴ tal./NMR 1 Cp Nr O (CH ₂ ) ₂ OMe Nr 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 (1H, s) 3 l-Me-Cp Nr O (CH ₂ ) ₂ OMe SO ₂ Me 0.9 (2H, m) 1.3 (2H, m) 1.4 (3H, s) 3.2 (3H, s) 3.4 (3H, s) 3.8 (2H, t) 4.4 (2H, t) 7.2 (1H, d) 8.0 (1H, s) 8.1 (1H, d) 4 Me Nr O (CH ₂ ) ₂ OMe SO ₂ Me 2.6 (3H, s) 3.3 (3H, s) 3.45 (3H, s) 3.8 (2H, t) 4.4 (2H, t) 7.2 (1H, d) 8.0 (1H, d) 8.1 (1H, s) 5 Cp CI O (CH ₂ ) ₂ OMe SO ₂ Me 81.4-82.6 <> C 6 iPr CI O (CH ₂ ) ₂ OMe SO ₂ Me 84.2-86.2OC 7 Me CI O (CH ₂ ) ₂ OMe SO ₂ Me 107.2-107.8 ° C 8 Cp Nr O (CH ₂ ) ₂ OMe SMe 94.4-94.8 ° C 10 Cp SO ₂ Me O (CH ₂ ) ₂ OMe Nr 104.2-105.2OC 11 Cp SMe O (CH ₂ ) ₂ OMe H 59-62 ° C

Note: Cp = cyclopropyl

EXAMPLE 2

To a solution of 5-cyclopropyl-4 [2-bromo-3- (2-methoxyethoxy) -4 methylsulphenylbenzoyl] isoxazole (1.9 g) in dichloromethane was added 3-chloroperoxybenzoic acid (50-60%) (1.3 g). meanwhile, the temperature was maintained at about -15 ° C. The mixture was stirred at -15 ° C for 1 hour and at room temperature for 1 hour. The solution was diluted with dichloromethane and washed with sodium bisulfite solution (2M) and then with water. The organic layer was dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness. The residue was purified by flash column chromatography eluting with a mixture of ethyl acetate and cyclohexane (1: 5) to give 5-cyclopropyl-4 [2-bromo-3- (2-methoxyethoxy) -4-methylsulfinylbenzoyl] isoxazole ( compound 9) (1.52 g) as a white solid, m.p. 86.2-87.0 ° C.

In a similar manner, the following compounds were prepared from suitably substituted starting materials:

5-cyclopropyl-4- (2-methylsulfinyl-3- (2-methoxyethoxy)] benzoylisoxazole (compound 12), mp 82 to 84 ° C;

5-cyclopropyl-4- [2-methylsulfonyl-3- (2-methoxyethoxy)) benzoylisoxazole (Compound 13), m.p. 111 to 114 ° C.

REFERENCE EXAMPLE 1

A mixture of 3-cyclopropyl-1- [2-bromo-3- (methoxyethoxy) -4-methylsulfonylphenyl) propane-1,3-dione (7.5 g) and triethylorthoformate (10.3 g) in acetic anhydride was stirred and heated at reflux for 3 hours. It was evaporated to dryness and the residue was treated with xylene and evaporated again to dryness to give crude 3-cyclopropyl-1- [2-bromo-3- (2-methoxyethoxy) -4methylsulfonylphenyl) -2-ethoxymethylenepropane-1,3-dione (8.5 g) as a dark brown oil that was not further purified.

In a similar manner, the following compounds were prepared (but not purified) from suitably substituted starting materials:

R ¹ R ² R3 R ⁴ Cp Nr O (CH ₂ ) ₂ OMe Nr 1-Me-Cp Nr O (CH ₂ ) ₂ OMe SO ₂ Me Me Nr O (CH ₂ ) ₂ OMe SO ₂ Me Cp Cl O (CH ₂ ) ₂ OMe SO ₂ Me iPr Cl O (CH ₂ ) ₂ OMe SO ₂ Me Cp Nr O (CH ₂ ) ₂ OMe SMe Cp SO ₂ Me O (CH ₂ ) ₂ OMe Nr Cp SMe ^: O (CH ₂ ) ₂ OMe H

Note: Cp = cyclopropyl

REFERENCE EXAMPLE 2

A mixture of crude t-butyl 2- [2-bromo-3- (2-methoxyethoxy) -4 methylsulfonylbenzoyl) -3-cyclopropyl-3-oxopropanoate (10.2 g) and 4-toluenesulfonic acid (2 g) in dry toluene was obtained stirred and heated at reflux for 2 hours. The cooled mixture was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 3-cyclopropyl-1 [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylphenyl] propane -1,3 dione (7.5 g) as a brown oil, NMR (CDClf 0.9 (4H, m), 1.5 (5H, 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).

The following compounds were prepared in a similar manner from suitably substituted starting materials.

R ² Ο Ο

Rl

Rl R ² R3 R ⁴ NMR / m.p. Cp Nr O (CH ₂ ) ₂ OMe Nr 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 (1H, d) 7.9 (1H, d) 1-Me-Cp Nr O (CH ₂ ) 2OMe 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 Nr O (CH ₂ ) 2OMe 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 Cl O (CH ₂ ) ₂ OMe SO ₂ Me ll (4H, m) 1.7 (lH, m) 3.3 (3H, s) 3.5 (3H, s), 3.8 (2H, t) 4.3 (2H, t) 5.9 (lH, s) 7.3 (lH, d) 7.7 (lH, d) iPr Cl O (CH ₂ ) 2OMe SO ₂ Me ll (6H, d) 2.4 (lH, m) 3.1 (3H, s) 3.3 (3H, s} 3.6 (2H, t) 4.2 (2H, t) 5.7 (lH, s) 7.1 (lH, d) 7.7 ( lH, d) Me Cl O (CH ₂ ) 2OMe SO ₂ 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) 8.0 (1H, d) Cp Nr O (CH ₂ ) 2OMe SMe 1.2 (4H, m) 1.8 (1H, m) 2.5 (3H, s) 3.5 (3H, s) 3.8 (2H, t) 4.2 (2H, t) 6.0 (1H, s) 7.1 (2H, m) Cp SO ₂ Me O (CH ₂ ) 2OMe Nr 1.0 (4H, m) 2.0 (1H, m) 3.3 (3H, s) 3.5 (3H, s) 3.9 (2H, t) 4.4 (2H, t) 5.75 (1H, s) 7.0 (1H, d) 7.7 ( lH, d) Cp SMe O (CH ₂ ) 2OMe H -

Note: Cp = cyclopropyl

REFERENCE EXAMPLE 3

Carbon tetrachloride (1ml) was added to a mixture of t-butyl-3cyclopropyl-3-oxopropionate (4.5 g) and magnesium (0.68 g) in methanol, which was stirred, resulting in a strong reaction. The mixture was stirred for 0.25 hours and evaporated to dryness. The residue was dissolved in acetonitrile and a solution of 2-bromo-3- (2 methoxyethoxy) -4-methylsulfonylbenzoyl chloride in acetonitrile (50 ml) was added and the resulting mixture was stirred at room temperature for 2 hours and allowed to stand overnight. Acetonitrile was removed under reduced pressure and the residue was suspended in toluene. The toluene suspension was washed with 2M HCl, then with water. The resulting organic solution was dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give crude tert-butyl 2- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl] -3-cyclopropyl-3-oxopropionate (10.27 g) as a crude brown oil .

The following compounds were prepared in a similar manner.

R ² OO

R ⁴ CO2tBu

R ¹ R ² R ³ R ⁴ The reaction. solvent Cp Nr O (CH ₂ ) ₂ OMe Nr ch ₃ cn 1-Me-Cp Nr O (CH ₂ ) ₂ OMe SO ₂ Me Toluene Me Nr O (CH ₂ ) ₂ OMe SO ₂ Me Toluene Cp Cl O (CH ₂ ) ₂ OMe SO ₂ Me CH ₃ CN iPr Cl O (CH ₂ ) ₂ OMe SO ₂ Me ch ₃ cn Me Cl O (CH ₂ ) ₂ OMe SO ₂ Me ch ₃ cn Cp Nr O (CH ₂ ) ₂ OMe SMe ch ₃ cn Cp SO ₂ Me O (CH ₂ ) ₂ OMe Nr ch ₃ cn Cp SMe O (CH ₂ ) ₂ OMe H ch ₃ cn

Benzoyl chlorides were prepared by heating suitably substituted benzoic acids with thionyl chloride at reflux for 3 hours.

REFERENCE EXAMPLE 4

Ethyl 2-bromo-3- (2-methoxyethoxy) -4-methylsulphenylbenzoate (24.3 g) was added to a solution of potassium hydroxide (9.1 g) in water (25 ml) and industrial burner spirit (300 ml). The resulting mixture was heated at reflux for 4 hours and then allowed to cool to room temperature overnight. The mixture was evaporated and the residue dissolved in water and washed with ether. The aqueous layer was acidified to pH 1 with 2M HCl and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 2-bromo-3- (2-methoxyethoxy) -4 methylsulfenyl benzoic acid (19.4 g) as a white solid, NMR (CDCl ₃ ) 2.2 (3H, s). 3.25 (3H, s), 3.6 (2H, t), 3.8 (2H, t),

7.0 (2H, m).

In a similar manner, we prepared, starting with ethyl

4-bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoate,

4-Bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoic acid as a white solid, m.p. 156-157.8 ° C.

REFERENCE EXAMPLE 5

Ethyl 4-bromo-3- (2-methoxyethoxy) -2-methylsulphenylbenzoate (5.0 g) was stirred in acetic acid (8 ml) and acetic anhydride (2.0 ml) at 0 ° C. Hydrogen peroxide (11 ml) was added to the mixture. The mixture was stirred at 0 ° C for 1 hour and then overnight at room temperature. Then the mixture was heated at 85 ° C for 1 hour. After cooling to room temperature, the mixture was diluted with ethyl acetate and washed with water, then with ferrous sulfate and again with water. The organic extract was dried (anhydrous MgSO ₄ ) and filtered. The filtrate was evaporated to dryness to give 4bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoate (4.7g) NMR (CDCl3) 1.8, (3H, t), 3.4 (3H, s). 4.15 (2H, t) 4.3 (2H, q),

4.6 (2H, t), 7.15 (H, d), 7.85 (1H, d).

REFERENCE EXAMPLE 6

Ethyl 2,4-dibromo-3- (2-methoxyethoxy) benzoate (32.2 g) was stirred in dimethylformamide (DMF) (80 ml) with potassium carbonate (36 g). A solution of methane thiol (13 ml) in DMF (20 ml) was added to the resulting suspension. The resulting mixture was stirred at room temperature overnight. It was then diluted with ether and the mixture was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness. The residue was purified by column chromatography on silica eluting with a mixture of ethyl acetate and cyclohexane (1:20) to give ethyl 4-bromo-3- (2-methoxyethoxy) -2-methylsulphenylbenzoate (3.5 g) as an oil which we did not further characterize.

REFERENCE EXAMPLE 7

- [3- (2-Methoxyethoxy-2-methylsulfenylphenyl) -4,4-dimethyl-2-oxol zoline (48.7 g) was added to 3M hydrochloric acid solution (700 ml) at 90 ° C. The mixture was stirred. at 90 ° C for 3 hours, cooled to room temperature and extracted with ethyl acetate. The organic extract was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 3- (2-methoxyethoxy-2 -methylsulfenylbenzoic acid as a golden oil (40.9 g), NMR (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

Solutions of 2- [3- (2-methoxyethoxy) phenyl '] -4,4-dimethyl-2-oxazoline (63.4 g) in tetrahydrofuran were cooled to -40 ° C under an inert atmosphere. N-Butyl lithium (125 ml, 2.5M) was added to the solution. The resulting mixture was stirred at -15 ° C for 1 hour and then cooled again to -40 ° C. Saturated ammonium chloride solution was added and the mixture was extracted with ether. The organic extract was washed with water, dried (anhydrous magnesium sulfate) and filters16. The filtrate was evaporated to dryness and the residue was recrystallized from hexane to give 2- [3- (2-methoxyethoxy) -2methylsulphenylphenyl] -4,4-dimethyl-2-oxazoline (56.5 g) as a powder, m.p. 44.4-46.4 ° C.

REFERENCES EXAMPLE 9

N- (2-hydroxy-1,1-dimethylethyl) -3- (2-methoxyethoxy) benzamide was stirred at 0 ° C. Thionyl chloride (90 ml) was added over 1 hour. The resulting solution was stirred at 15 ° C for a further 1.5 hours and dry diethyl ether was added. The excess solvent was removed in vacuo and the residue suspended in diethyl ether, washed with 2M sodium hydroxide solution and the organic phase separated. The organic extract was washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness, leaving a residue which was distilled under reduced pressure to give 2- [3- (2-methoxyethoxy) phenyl)

-4,4-dimethyl-2-oxazoline (66 g) with boiling. 164-168 ° C at 199.95 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- (2methoxyethoxy) benzoyl chloride (67.8 g) in dichloromethane was added and the solution was stirred overnight at room temperature; during this time a precipitate formed. The mixture was filtered and the filtrate evaporated to dryness to give N- (2-hydroxy-1,1-dimethylethyl) -3- (2 methoxyethoxy) benzamide (95.9 g) as a syrup, NMR: CDCl-1, 4 (6H, s), 3.5 (2H, s), 3.65 (2H, s), 3.7 (2H, t), 4.2 (2H, t),

5.4 (1H, s), 6.3 (1H, s), 7.0 (1H, m), 7.3 (2H, m).

REFERENCE EXAMPLE 11

- (2-methoxyethoxy) benzoic acid (72.9 g) and thionyl chloride (119 g) were heated together under reflux for 1.5 hours and then allowed to cool overnight. Thionyl chloride was evaporated under reduced pressure. The residue was distilled under reduced pressure to give 3- (2-methoxyethoxy) benzoyl chloride (67.7 g), boiling. 130 ° C / 53.32 Pa.

REFERENCE EXAMPLE 12

2-Methoxyethyl 3- (2-methoxyethoxy) benzoate (133 g) was dissolved in an industrial burner spirit and 2M sodium hydroxide solution and heated to reflux for 1.5 hours. The mixture was 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 the resulting mixture filtered. The residue was washed with water and air-dried. The residue was recrystallized from ether and petroleum (boiling point 40-65 ° C) to give 3- (2-methoxyethoxy) benzoic acid (86 g) as a white solid from the ground. 79.6-81.8 ° C.

REFERENCE EXAMPLE 13

3-Hydroxybenzoic acid (73 g) was dissolved in dimethyl formamide and potassium carbonate (160 g). 2 Chloroethyl methyl ether (200 g) and potassium iodide (8.8 g) were added. The mixture was heated at 72 ° C for 42 hours. After cooling, the mixture was poured onto ice and extracted with ether. The organic extract was washed with 2M sodium hydroxide solution, water, brine and dried (anhydrous magnesium sulfate) and filtered. The filtrate was evaporated to dryness to give 2-methoxyethyl 3- (2methoxyethoxy) benzoate (135.5 g), which was not further purified.

According to a feature of the present invention, there is provided a method of controlling weed growth on the ground (i.e., undesirable vegetation), comprising administering to herbicidally effective amounts of at least one isoxazole derivative of general formula (I) therein. To this end, isoxazole derivatives are commonly used in the form of herbicidal compositions (i.e., combined with compatible solvents or carriers and / or surfactants suitable for use in herbicidal compositions), for example as described hereinafter.

Compounds of general formula (I) exhibit herbicidal activity against weed (weed) and weed (weed) when applied before and / or after germination.

The term pre-emergence application means an application to the earth in which weed seeds or sprouts are present before weeding occurs above the soil surface. The term application after germination means application to surface or exposed parts of weeds that have already appeared above the soil surface. For example, compounds of general formula (I) can be used to control growth:

broad-leaved weeds, for example, Abutilon theophrasti, Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. e.g. Ipomea purpurea, Sesbania exaltata, Sinapis arvensis, Solanum nigrum and Xanthium strumarium, and grass weeds, for example, Alopecurus mysouroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Sorghum bicolis, Setus traria and Setusaria fabaria, Setus tricaria or Setusaria fabaria , for example, Cyperus esculentus.

The amounts of the compounds of general formula (I) used vary depending on the nature of the weed, the composition used, the application time, climatic and edaphic conditions, and (when used to control weed growth in crop growing areas) the nature of the crop. When used on arable crops, the dose should be sufficient to control weed growth without causing significant permanent damage to the crop. In general, when taken into account, these factors produce good dose results between 0.01 kg and 5 kg of active substance per hectare. However, it should be understood that larger or smaller doses may be required depending on the particular problem of weed control.

Compounds of general formula (I) can be used to selectively control weed growth, for example, to control the growth of those species previously mentioned, by application before or after sprouting in a direct or indirect way, e.g. through the direct or direct sprinkling of weed-infested land used or intended for crop production, for example cereals, e.g. cereals, barley, oats, corn and rice, soybeans, field and dwarf beans, peas, alfalfa, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflowers, beet and grass, whether or not sown , before or after sowing the crop or before or after sprouting the crop. For the selective control of weeds on land that has been attacked by weeds and used or intended for cultivation of crops, e.g. The crops mentioned earlier are particularly suitable doses between 0.01 kg and 4.0 kg, with preference being given to amounts between 0.01 kg and 2.0 kg, of the active substance per hectare.

The compounds of general formula (I) may also be used to control weed growth, in particular that previously indicated, by application before or after sprouting in landscaped orchards and other areas where trees are grown, such as rainforests, forests and parks, and plantations, e.g. sugar cane, palm oil or gum plantations. For this purpose, they can be applied directly or indirectly (eg by direct or indirect spraying) to weeds or land where it is expected to occur, before or after planting trees or plantations, in doses between 0.25 kg and 5.0 kg , preference is given to quantities between 0.5 and 4.0 kg, of the active substance per acre.

Compounds of general formula (I) can also be used to control weed growth, especially the one previously indicated, in areas other than crop growing areas, but weed control is desirable.

Examples of non-arable crops include meadows, industrial sites, railways, roadside edges, riverbanks, irrigation and other waterways, bushes and fallow land or arable land, especially where weed control is desirable, would reduce the risk of fires. When used for such purposes for which full herbicide action is often desirable, the active compounds are normally administered at doses higher than those used on crop areas, as described previously. The precise dosage will depend on the vegetation being cultivated and the effect sought.

For this purpose, applications prior to or after germination are particularly suitable, the application being preferred over germination, in a direct or indirect manner (eg by direct or indirect spraying) at doses between 1.0 kg and 20.0 / kg, between 5,0 and 10,0 kg of active substance per hectare.

When used to control weed growth through pre-sprout application, compounds of general formula (I) can be incorporated into the soil where weeds are expected to emerge. It will be appreciated that when to control weed growth by application after germination, ie. applications to surface or exposed parts of weed that have sprouted we use compounds of general formula (I), these same compounds will normally come in contact with the soil and will then also be able to cause soil to sprout in the soil after sprouting.

Where particularly extended weed control is required, the administration of the compounds of general formula (I) may be repeated as necessary.

According to a further feature of the present invention, compositions suitable for herbicidal use containing one or more isoxazole derivatives of general formula (I) are combined, and preferably homogeneously dispersed in one or more compatible diluents or carriers and / or surfactants acceptable to agriculture (i.e., diluents or carriers and / or surfactants of a type generally accepted in the art as suitable for use in herbicidal compositions and compatible with compounds of general formula (I)). The term “homogeneously dispersed is used to include compositions in which compounds of general formula (I) are dissolved in other components. The term herbicidal composition has been used for the 21st century in the broad sense of the word, to include not only compositions prepared for use as herbicides, but also concentrates that must be diluted before use. Preference is given to compositions containing from 0.05 to 90% by weight of one or more compounds of general formula (I).

Herbicidal compositions may contain both a diluent or carrier, and a surfactant (e.g., a wetting agent that permits dispersion or emulsification). The surfactants that may be present in the herbicidal compositions of the present invention may be ionic or non-ionic species, for example sulforicinoleates, quaternary ammonium derivatives, products based on ethylene oxide condensates with alkyl or polyaryl phenols, e.g. nonyl or octylphenols, or carboxylic acid anhydrosorbitol esters which, by the etherification of free hydroxy groups by condensation with ethylene oxide, are soluble alkali and alkaline earth metal salts of sulfuric acid and sulfonic acids such as dinonyl and dioctyl sulfonate ethers and alkali metal or alkaline earth metal salts of high molecular weight sulfonic acid derivatives such as sodium and calcium lignosulfonates and sodium and calcium alkylbenzene sulfonates.

Suitably, the herbicidal compositions according to the present invention may contain up to 10% by weight, e.g. from 0.05% by weight to 10% by weight of the surfactant but, if desired, the herbicidal compositions according to the present invention may contain a higher ratio of surfactant, for example up to 15% by weight, in concentrates of suspensions which can be emulsified in a liquid and up to 25% by weight in water-soluble liquid concentrates.

Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesium, kieselguhr, tricalcium phosphate, powdered cork, adsorbent black carbon and clays such as kaolin and bentonite. In the preparation of solid compositions (which may take the form of powders, granules or wettable powders), preference is given to grinding compounds of general formula (I) with solid diluents or impregnating solid diluents or carriers with solutions of compounds of general formula (I) in volatile solvents. to allow the solvent to evaporate and, if necessary, grind the products to obtain powders. Granular formulations can be prepared by absorbing compounds of general formula (I) (dissolved in suitable solvents which, if desired, are volatile) in solid diluents or granular carriers and, if desired, allowing the solvents to evaporate, or by granulating the powder formulations obtained as described above. Solid herbicidal compositions, especially wettable powders and granules, may contain wetting or dispersing agents (for example, of the species described above) that can serve, when solid, as diluents or carriers.

The liquid compositions of the invention may take the form of aqueous, organic, or aqueous-organic solutions, suspensions, and emulsions, which may include a surfactant. Liquid diluents suitable for incorporation into liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal or vegetable oils, and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). The surfactants that may be present in the liquid compositions may be ionic or non-ionic (for example, the types described above) and, when liquid, may also serve as diluents or carriers.

Powders, dispersible granules and concentrate liquid compositions may be diluted with water or other suitable diluents to obtain a ready-to-use composition, for example mineral or vegetable oils, especially in the case of liquid concentrates in which the diluent or carrier is an oil. e.

When desired, the liquid compositions of the compounds of general formula (I) can be used in the form of self-emulsifying concentrates containing active substances dissolved in emulsifying agents that are compatible with the active substances of the ready-to-use composition by simple administration. water with such concentrate.

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

The herbicidal compositions of the present invention may also contain, if desired, conventional additives such as adhesives, protective colloids, thickeners, penetrating agents, stabilizers, separators, anti-clotting agents, colorants and corrosion inhibitors. These additives can also serve as carriers or thinners.

Unless otherwise specified, the following percentages are by weight. Preferred herbicidal compositions according to the present invention are:

concentrates in the form of a suspension in water containing from 10 to 70% of one or more compounds of general formula (I), from 2 to 10% of surfactant, from 0.1 to 5% of thickener and from 15 to 87, 9% water;

wettable powders containing from 10 to 9% by weight of one or more compounds of general formula (I), 2 to 10% of surfactant and 8 to 88% of a solid diluent or carrier;

powders which may be soluble or dispersible in water, containing from 10 to 9 0% of one or more compounds of general formula (I), from 2 to 40% of sodium carbonate and from 0 to 88% of a solid diluent;

water soluble liquid concentrates containing from 5 to 50%, e.g. 10 to 30%, of one or more compounds of general formula (I), 5 to 25% of surfactant and 25 to 90%, e.g. 45 to 85%, water miscible solvent, e.g. dimethylformamide, or a mixture of miscible water and water miscible;

liquid concentrates in the form of an emulsifiable suspension containing from 10 to 7 0% of one or more compounds of general formula (I), from 5 to 15% of surfactant, from 0.1 to 5% of thickener and from 10 up to 84.9% organic solvent;

granules containing from 1 to 90%, e.g. 2 to 10% of one or more compounds of general formula (I), from 0.5 to 7%, e.g. 0.5 to 2%, surfactant and 3 to 98.5%, e.g. 88 to 97.5% of the granular carrier and emulsifiable concentrates containing from 0.05 to 90%, preferably from 1 to 60%, of one or more compounds of general formula (I) from 0.01 to 10%, preferably from 1 to 10%, surfactant and from 9.99 to 99.94%, preferably from 39 to 98.99%, of an organic solvent.

The herbicidal compositions of the present invention may also contain compounds of general formula (I) combined with, and, if possible, homogeneously dispersed, in one or more pesticidally active compounds and, if desired, with one or more compatible, pesticide-acceptable diluents or carriers , surfactants and conventional additives such as those described earlier herein. Examples of other pesticidally active compounds that can be included in, or used in combination with, the herbicidal compositions of the present invention include herbicides, for example, to increase the range of weed species to be controlled, such as alachlor [2-chloro-2,6 -diethyl-N- (methoxy-methyl) -acetanilide), atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5 triazine), bromoxynil [3,5-dibromo-4-hydroxybenzonitrile], chlortoluron (N '- (3-chloro-4-methylphenyl) -N, N-dimethylurea), cyanazine- [2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5 triazine ), 2,4-D [2,4-dichlorophenoxyacetic acid), dicamba [3,6-dichloro-2-methoxybenzoic acid), difenzoquate [1,2dimethyl-3,5-diphenylpyrazolium salts), flampromethyl [methyl N -2- (N-benzoyl-3-chloro-4-fluoroanilino) -propionate), fluometuron [N '- (3-trifluoro-methylphenyl) -N, N-dimethylurea), insecticides, e.g. synthetic pyrethroids, e.g. permethrin or cypermethrin, and fungicides, e.g. carbamates, e.g. methyl N- (1-butyl-carbamoyl25 benzimidazol-2-yl) carbamate, and triazoles, e.g. 1- (4-Chlorophenoxy) 3,3-dimethyl-1,2,4-triazol-1-yl) -butan-2-one.

Pesticide-active compounds and other biologically active substances that can be included in, or can be used in combination with, the herbicidal compositions of the present invention, for example those mentioned earlier and which are acids, can be used if desired in the form of conventional derivatives, for example alkali metal salts and amine salts and esters.

According to a further feature of the present invention, a product containing at least one of the isoxazole derivatives of the general formula (I) or, preferably, a herbicidal composition as described above is provided, and a herbicidal concentrate is preferred which must be diluted before use, which contains at least one of the isoxazole derivatives of general formula (I), in the package for the aforementioned derivative or derivatives of general formula (I) or said herbicidal composition, with reference to how we use the aforementioned derivative or derivatives of the general formula to control weeds (I) or the herbicidal compositions contained therein. The packaging will normally be of the kind conventionally used to store chemical substances that are solid and herbicidal compositions at normal ambient temperature, especially in the form of concentrates, such as metal cans and lacquers, and plastic substances, bottles or glass and plastic materials and, where the contents of the packaging are solid - for example, granular herbicide compositions - boxes, such as cardboard, plastics and metal, or bags. Packaging will normally be of sufficient capacity to contain such quantities of isoxazole derivatives or herbicidal compositions sufficient to cultivate at least 0.4 hectares of soil to control the growth of weeds therein, but will not exceed a size that is consistent with conventional handling procedures. Referrals will be physically combined with the packaging, for example by printing directly on it or on a label or tag attached to it. The instructions will normally indicate that the contents of the packaging, after dilution if necessary, are intended to control the growth of weeds at doses between 0.01 kg and 20 kg of the active substance per hectare, in the manner and for the purposes described earlier in this text.

The following examples illustrate the herbicidal compositions of the present invention:

EXAMPLE Cl

The soluble concentrate is formed from:

Active ingredients (compound 1) 20% w / v

Potassium hydroxide solutions, 33% w / v 10% v / v

Tetrahydrofurfuryl alcohol (THFA) 10% v / v

Water up to 100 volumes by mixing THFA, active ingredient (Substance 1) and 90% by volume of water and slowly adding potassium hydroxide solution until a stable pH of 7-8 is obtained and then replenished to the required volume with water.

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

EXAMPLE C2

Zones iv powder is formed from:

Active ingredients (compound 1) 50% w / w Sodium dodecylbenzene sulfonate 3% w / w Sodium lignosulfate 5% w / w Sodium formaldehyde alkylnaphthalene sulphonate 2% w / w Microfine silica 3% w / w Chinese clay 37% w / w by mixing all the above ingredients and grinding the mixture in an air jet mill.

Similar wettable powders can be prepared as previously described by replacing isoxazole (compound 1) with other compounds of general formula (I).

EXAMPLE C3

Water soluble powder is formed from:

Active Ingredients (Compound 1) 50% w / w Sodium dodecylbenzenesulfonate 1% w / w Microfine silica 2% w / w Sodium bicarbonate 47% w / w by mixing said ingredients and grinding said mixture in a hammer mill.

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

The compounds of this invention have been used in herbicidal applications according to the following procedures.

PROCEDURE FOR USE OF HERBICID COMPOUNDS

a) The general part

Suitable amounts of the compounds used for the treatment of the plants are dissolved in acetone to give solutions equivalent to doses of up to 4000 g of test substance per hectare (g / ha). These solutions are applied with a standard laboratory herbicide sprayer, which emits an equivalent of 290 liters of fluid per hectare.

b) Weed control: before sprouting

The seeds are sown in 70 mm deep and 75 mm deep plastic pots in non-sterile soil. The quantities of seeds per pot were as follows:

Type of weed Approximate number of seeds per pot

1) Broad-leaved weeds

Abutilon theophrasti Amaranthus retroflexus Galium aparine Ipomoea purpurea Sinapis arvensis Xanthium strumarium

2) Grass weed

Alopecurus myosuroides Avena fatua

Echinochloa crus-galli Setaria viridis

3) Cod

Cyperus esculentus

A field of shit

Approximate number of seeds per pot

1) Broadleaf

Cotton

Soybeans

2) Grasses

Maize 2 Rice 6 Wheat 6

The compounds of the invention were applied to a soil surface containing seeds as described in (a). We assigned a single pot to each cultivation for each crop and each weed; controls were not sprayed or sprayed with acetone alone.

After treatment, the crucibles were placed on a capillary mat in a greenhouse and watered above. Field crop damage was visually assessed 20 to 24 days after spraying. The results were expressed as a percentage reduction in growth or damage to crops or weeds, compared to plants in control pots.

c) Weed control: after germination

Weeds and crops were sown directly in John Innes potting compost into 75 mm 7 7 mm square pots except Amaranthus, which was torn off in the germ state and transferred to pots one week before spraying. The plants were grown in the greenhouse until they were ready to be sprayed with the compounds used to process them. The number of plants per pot was as follows:

1) Weeds with broad leaves

A kind of weed Number of plants per pot Growth phase Abutilon theophrasti 3 1-2 list Amaranthus retrflexus 4 1-2 list Galium aparine 3 1st turn Ipomoea purpurea 3 1-2 list Sinapis arvensis 4 2 sheets Xanthium strumarum 1 2-3 sheets

2) Grass weed Growth phase A kind of weed Number of plants per pot Alopecurus myosuroides 8-12 1-2 list Avena fatua 12-18 1-2 list Echinochloa crus-galli 4 2-3 sheets Setaria viridis 15-25 1-2 list 3) Cod A kind of weed Number of plants Growth phase per pot

Cyperus esculentus leaf

1) Broadleaf

A field of rags

Number of plants per pot

Growth phase

Cotton

Soybeans

2-3 sheets

2-3 sheets

2) Grasses

A field of rags

Number of plants per pot

Growth phase

Maize 2 2-3 list Rice 4 2-3 list Wheat 5 2-3 list

The compounds used for the treatment of the plants were applied to the plants as described in (a). For each treatment, a single pot of each crop and weed species was ordered, with controls that were not sprayed and controls that were sprayed with acetone only.

After the treatment was completed, the crucibles were placed on the capillary mat in the greenhouse and watered from above once every 24 hours and then by controlled subirigation e. Field crop damage and weed control were visually assessed 20-24 days after spraying. The results were expressed as a percentage reduction in growth or damage to crops or weeds, compared to plants in control pots.

The compounds of the invention showed an excellent level of herbicidal activity on weeds used in the aforementioned experiments, together with crop tolerance.

Compounds 1 to 35 cause at least 90% reduction in growth of one or more weeds when applied before or after germination in an amount of 1000 g / ha.

For

RHONE-POULENC AGRICULTURE LTD:

rater office

LJUBLJANA , "

Claims (11)

1. 4-Benzoylisoxazole derivatives of general formula (I): in which R ¹ represents a straight- or branched-chain alkyl or alkoxyl group containing up to four carbon atoms, or a tri- or four-membered cycloalkyl group optionally substituted with a straight or branched chain containing up to four carbon atoms; O R R R represents a halogen atom, a group selected from R, -OR, -S (O) _m R ⁵ , -O (CH 2) -OR ⁵ , -CO ² R ⁵ and nitro; R represents a halogen atom or a group selected from R, -OR ⁵ , -S (O) mR ⁵ and -O (CH 2) _q -O R ⁵ ; R ⁴ represents a hydrogen or halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) mR ⁵ , -O (CH 2) _q -OR ⁵ and nitro; provided that at least one of the groups R ² , R ³ and R ⁴ is -O (CH ₂ ) _q -OR ⁵ ; R ⁵ represents a straight or branched chain alkyl or alkoxyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; ' m means zero, one or two; and q is an integer from one to three. Oh A compound according to claim 1, wherein R is -O (CH ₂ ) _q -O R ⁵ . A compound according to claim 1 or 2, characterized in that R represents a halogen atom or a group selected from R, -OR ⁵ , -S (O) m R ⁵ , -CO ² R ⁵ and nitro; R ³ is -O (CH ₂ ) g-OR ⁵ ; R ⁴ represents a hydrogen or halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) _m R ⁵ and nitro; and q means two or three. Compound according to claim 1, 2 or 3, characterized in that it has one or more of the following characteristics: R ¹ represents a methyl, ethyl, 1-methylethyl, cyclopropyl or 1-methylcyclopropyl group; R ⁴ represents a chlorine, bromine or fluorine atom, or a group selected from R ⁵ and -S (O) _m R ⁵ ; R ⁵ represents a straight or branched chain alkyl or alkoxyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms. A compound according to any one of the preceding claims, characterized in that it has one or more of the following characteristics: R ¹ represents a 1-methylethyl, 1-methylcyclopropyl or cyclopropyl group; R ⁵ represents a methyl, ethyl or trifluoromethyl group, at least one of R ² and R ⁴ represents -S (O) _m CH ₃ , provided that R ² and R ⁴ do not simultaneously represent -SO ₂ CH ₃ ; q means two. A compound according to any one of the preceding claims, characterized in that: R ¹ represents a cyclopropyl group; R represents a chlorine, bromine or fluorine atom, or a group selected from methyl, trifluoromethyl and -S (O) _m CH ₃ ; R ³ is -O (CH ₂ ) _q -O R ⁵ ; R ⁴ represents a chlorine, bromine or fluorine atom, or a group selected from methyl, trifluoromethyl and -S (O) _m R ⁵ ; at least one of the groups R ² and R ⁴ is -S (O) mCH ₃ , provided that R ² and R ⁴ do not simultaneously represent -SO ₂ CH ₃ ; and q means two. A compound according to claim 1 or 2, characterized in that 1θ 4- [2,4-Dibromo-3- (2-methoxyethoxy) benzoyl) -5-cyclopropylisoxazole; 4- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5-cyclopropylisoxazole; 4- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5- (1-methylcyclopropyl) isoxazole; 4-1 2-Bromo-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5-methylisoxazole; 4- [2-chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5-cyclopropylisoxazole; 4- [2-chloro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5-isopropylisoxazole; 4-fluoro-3- (2-methoxyethoxy) -4-methylsulfonylbenzoyl) 5-methylisoxazole; 4- [2-bromo-3- (2-methoxyethoxy) -4-methylsulphenylbenzoyl) 5-cyclopropylisoxazole; 4- [2-bromo-3- (2-methoxyethoxy) -4-methylsulfinylbenzoyl) 5-cyclopropylisoxazole; 4- (4-bromo-3- (2-methoxyethoxy) -2-methylsulfonylbenzoyl) 5-cyclopropylisoxazole; 5- cyclopropyl-4- [2-methylsulphenyl-3- (2-methoxyethoxy) benzoylisoxazole; 5-cyclopropyl-4- [2-methylsulfinyl-3- (2-methoxyethoxy) benzoylisoxazole; and 5-Cyclopropyl-4-yl 2-methylsulfonyl-3- (2-methoxyethoxy) benzoylisoxazole. A process for the preparation of a compound of general formula (I) as defined in claim 1, characterized in that it comprises: a) reaction of a compound of general formula (II): (Π) wherein R ¹ , R ² , R ³ and R ^{4 are} as defined in claim 1 and L is a leaving group with a hydroxylamine salt. b) reaction of a compound of general formula (III): in which R ^{1 is} as general formula (IV): is specified in the claim 1, with the compound of which R ² , R ³ and R ⁴ as defined in claim 1; c) reaction of a compound of general formula (V): Y (V) wherein R ^{1 is} as defined in claim 1 and Y represents a carbos group or a reactive derivative thereof or a cyano group, with a suitable organometallic reagent; A herbicidal composition comprising as an active ingredient an herbicidally effective amount of a 4-benzoylisoxazole derivative of general formula (I) as defined in any one of claims 1 to 7 together with a diluent or carrier and / or surfactant, which are acceptable for agriculture. A method of controlling weed growth on a land, characterized in that it comprises the application of a herbicidally effective amount of a 4-benzoylisoxazole derivative of general formula (I) as defined in any one of claims 1 to 7. Method according to claim 10, characterized in that the land is used or intended to be used for crop cultivation and that the compound is applied at doses from 0.01 kg to 4.0 kg per hectare. For FHONE-POULENC AGRICULTURE LTD: LJUBLJANA PATENT OFFICE · Excerpt 4-BENZOYLISOXAZOLE DERIVATIVES USED AS HERBICIDES Described are the 4-benzoylisoxazole derivatives of general formula (I): (I) in which R ¹ represents an alkyl group or an optionally substituted cycloalkyl group; R represents a halogen atom, a group selected from R, -OR ⁵ , -S (O) _m R ⁵ , -O (CH 2) -OR ⁵ , -CO ² R ⁵ and nitro. R represents a halogen atom or a group selected from R, -OR ⁵ , -S (O) mR ⁵ and -O (CH 2) _q -O R ⁵ ; R ⁴ represents a hydrogen or halogen atom or a group selected from R ⁵ , -OR ⁵ , -S (O) mR ⁵ , -O (CH 2) g-OR ⁵ and nitro; provided that at least one of the groups R ² , R ³ and R ⁴ is -O (CH ₂ ) _g -O R ⁵ ; R ⁵ means an straight or branched chain alkyl or alkoxyl group containing up to four carbon atoms,