Derivatives of 5-arylisoxazoles, methods for their preparation, herbicide composition and method for suppressing weeds in the locus

 

(57) Abstract:

Usage: in agriculture as herbicides. The inventive product-derived 5-arylisoxazoles f-crystals 1 with certain values radicals. The formation of compounds 1 are three ways. Herbicide composition comprising an effective amount of compounds f-crystals 1 and the target additive and the method of suppressing weeds in the locus with the use of the herbicide compounds f-ly 1:

< / BR>
6 S. p. f-crystals, 5 C. p. F.-ly, 5 PL.

The invention relates to derivatives of 5-aryl-isoxazol of, compositions containing them, methods for their preparation and their use as herbicides. U.S. patent N 4173650 discloses 4-acetyl-5-(4'-forfinal)isoxazol, which is used as an intermediate substance in the formation of compounds that have anti-inflammatory action. L. I. Smith and others (JACS, 1959, Vol. 59, 1078-1083) describes the connection is obtained, which is considered 4-acetyl-3-methyl-(2', 3', 4', 5',6'-pentamethyl - nil)isoxazol. None of these publications disclose the use of these compounds as herbicides. In the Belgian patent N 880849 describes 5-aryl isoxazole compositions that can be used as preventing harm to the r phenyl group, substituted with one to five groups of R2or pridelava group not substituted or substituted by one to four groups R2,

R is hydrogen, -CO2R3, -COR4, cyano, halogen, or alkyl group with straight or branched chain containing up to 4 carbon atoms, optionally substituted by one or more atoms of halogen,

R1an alkyl group with straight or branched chain containing up to 6 carbon atoms which may be substituted by one or more halogen atoms or cycloalkyl group containing from 3 to 6 carbon atoms, or cycloalkyl group containing from 3 to 6 carbon atoms, optionally substituted by one or more groups R4or one or more atoms of halogen,

R2halogen atom, R4, nitro, -CO2R3, -OR4, -S(O)mR4, -S(O)mR5-O-(CH2)p-OR4or an alkyl group with straight or branched chain containing up to 6 carbon atoms, substituted-or SIG4,

R3and R4that may be the same or different, each represents an alkyl group with straight or branched chain containing up to 6 carbon atoms, optionally substituted by one or more atoms is s, nitro, R4and-OR4;

p is an integer from 1 to 3;

m is 0, 1 or 2, provided that

(a) when R is hydrogen, R1methyl, Ar is not 4-florfenicol,

(b) if R and R1both represent methyl, Ar is not 2,3,4,5,6-pentamethylbenzyl, which has valuable herbicide properties.

In some cases, the substituents R, R1, R2and R4improve optical isomerism and/or stereometria. All such forms are embraced by the invention.

Compounds in which R is hydrogen, R1methyl and Ar is 4-forfinal, and compounds in which R and R1methyl, Ar 2,3,4,5,6-pentamethylbenzyl are not considered part of the invention, but compositions containing them and their use as herbicides, are considered part of the invention.

A preferred class of compounds of formula (I) due to their herbicide properties are those in which Ar represents a phenyl group substituted by one to five groups, R2and R2halogen atom, R4, nitro, -CO2R3, -OR4, -S(O)mR4, -O-(CH2)p-OR4or alkyl group with straight or branched chain containing up to 6 carbon atoms, which is substituted-or SIG4.

Other predpochtitel the CO2R3or fulfills I TS cor4and/or

(b) Ar represents a phenyl group substituted by one to three groups R2.

Another preferred class of compounds of General formula (I) are those in which

Ar represents a phenyl group substituted by one or two groups R2and/or meridiabuy group substituted by a group S(O)mR4,

R is hydrogen or-CO2R3< / BR>
R1cyclopropyl,

R2group selected from halogen, R4, -S(O)mR4and-S(O)mR5.

The most important compounds include the following:

1. 4-cyclopropanecarbonyl-5-(2-fluoro-4-methylsulfinylphenyl)isoxazol;

2. 4-cyclopropanecarbonyl-5-(3,4-di-chlorophenyl)isoxazol;

3. 4-cyclopropanecarbonyl-5-[4-(methylsulfinyl)phenyl]isoxazol;

4. 4-cyclopropanecarbonyl-5-[3-chloro-4-(methylsulfanyl)phenyl]isoxazol;

5. 4-cyclopropanecarbonyl-5-[3-chloro-4-(methylsulphonyl)phenyl]isoxazol;

6. 4-cyclopropanecarbonyl-5-[4-(methylsulphonyl)phenyl]isoxazol;

7. 4-cyclopropanecarbonyl-5-[4-(methylsulfinyl)phenyl]isoxazol;

8. 4-cyclopropanecarbonyl-5-[3-(methylsulfanyl)phenyl]isoxazol;

9. ethyl 5-[2-chloro-4-(methylsulfinyl)phenyl] -4-cyclopropyl-carbonyloxy - C is kilat;

11. 1-methylethyl-4-cyclopropanecarbonyl-5-[2-(methylsulfanyl)-4-trifluoromethyl - phenyl]isoxazol-3-carboxylate;

12. 4-cyclopropanecarbonyl-5-[2-(phenylsulfanyl)-4-triptoreline]ISO - xazal;

13. 4-cyclopropanecarbonyl-5-[5-(methylsulfanyl)pyrid-2-yl]isoxazol.

The described methods can also obtain compounds of General formula (I), are given in table.1.

Compounds of General formula (I) can be obtained by application or adaptation of known methods, for example methods described herein.

Compounds of General formula (I) can be obtained by substitution of metal hydrogen compounds of General formula (II):

in which X is a halogen atom, with subsequent reaction of the thus obtained compound with an acid chloride of the General formula R1COCl. Usually X is bromine or iodine, and the reaction is carried out, for example, with n-butyllithium in an inert solvent (ether or tetrahydrofuran) at a temperature of from -78 to 0aboutC.

Compounds of General formula (I) can be obtained by oxidation of compounds of General formula (III):

to convert the hydroxyl group to a ketone group. The reaction is usually carried out, for example, using a mixture obtained from chromium trioxide and water sulphuric acid.

In addition, compounds of General formula (I) in which R is a hydrogen atom, can be obtained by reaction of compounds of General formula (V):

ArRin which L is leaving group-O-alkyl or N,N-dialkyl salt of hydroxylamine. Usually the preferred hydroxylamine hydrochloride. The reaction is usually conducted in a solvent (ethanol or acetonitrile) in the presence of a base or acid acceptor (triethylamine or sodium acetate).

Compounds of General formula (I) in which R is not a hydrogen atom, can be obtained by reaction of compounds of General formula (VI):

Ar R1where R is a leaving group, such as N,N-dialkyl or S-alkyl, with a compound of General formula RC(X)=N-OH, where X is as defined above; R is hydrogen. Usually X is chlorine or bromine.

The reaction is usually conducted in an inert solvent (such as toluene or dichloromethane) or in the presence of a base (such as the Nacu invention compounds of General formula (I), in which R is not hydrogen, can be obtained by reaction of compounds of General formula (VII)

Ar-C C-R1c compound of General formula RC(X)=N-OH, where X is as defined previously and R is not hydrogen. Usually X is chlorine or bromine.

The reaction is usually conducted in an inert solvent (such as toluene or dichloromethane), possibly in the presence of a base (such as triethylamine) or catalyst (such as 4A molecular sieve or ion fluoride).

In accordance with another characteristic of the invention compounds of General formula (I) in which R is not hydrogen, can be obtained by the reaction of salts of compounds of formula (VIII):

Ar R1with a compound of General formula RC(X)=NOH, where X is as defined above and R is hydrogen. Usually X is chlorine or bromine. Preferred salts include salts of sodium and magnesium.

Intermediate compounds used in the preparation of compounds of General formula (I) can be obtained by application or adaptation of known methods.

Compounds of General formula (III) can be obtained by substitution of metal hydrogen compounds of General formula (II), for example n-butyllithium in an inert solvent, such as ether or tetrahydrofuran at temperatures between -78aboutWith 0aboutWith subsequent reaction with an aldehyde of General forino be obtained by reaction of compounds of General formula (IX)

Ar where Y1CO2-alkyl or-CN, and L is as defined previously, with a salt of hydroxylamine such as hydroxylamine hydrochloride, in a solvent such as ethanol or acetonitrile, possibly in the presence of a base or acid acceptor such as triethylamine or sodium acetate.

Compounds of General formula (IV) in which Y represents a carboxylic acid or carboxylic acid chloride, can be obtained from the corresponding compounds of General formula (IV) in which Y represents the group of carboxylic ester, hydrolysis of the specified broadcasting group and converting the thus obtained acid into an acid chloride, for example, by heating with thionyl chloride.

Compounds of General formula (IX) can be obtained by reaction of keeeper or ketonitriles General formula (X):

Ar where Y1as defined previously, or trialkylaluminium (for example, triethylorthoformate) in the presence of acetic anhydride at a temperature of heating under reflux a mixture or dialkylimidazolium (for example, dimethylphenylpiperazinium) in an inert solvent, such as toluene, at a temperature of from room temperature to the temperature of heating under reflux of the mixture.

Conn is receiving General formula RC(X)=N-OH, where X is as defined previously and R is not hydrogen. Usually X is chlorine or bromine.

Compounds of General formula can be obtained by reaction of compounds of General formula (VIII) or trialkylaluminium (for example, triethylorthoformate) in the presence of acetic anhydride at a temperature of heating under reflux a mixture or dialkylimidazolium (for example, dimethylphenylpiperazinium) in an inert solvent such as toluene at a temperature from room temperature to the temperature of heating under reflux of the mixture.

Compounds of General formula (VI) can be obtained by reaction of compounds of General formula (XI)

Ar CH2where R is as previously defined, with an acid chloride of the General formula R1COCl in an inert solvent, such as dichloromethane or toluene in the presence of a base such as triethylamine.

Compounds of General formula (VII) can be obtained by metallation of the corresponding acetylene General formula (XII):

Ar-C C-X1where X1represents a hydrogen or halogen (e.g. bromine) using, for example, n-utility in an inert solvent, such as ether or tetrahydrofuran at a temperature of from -78 to 0aboutWith subsequent treatment of the acid chloride of General formula (XIII)

for example, by heating with bromine or iodine in the presence of concentrated nitric acid.

Compounds of General formula (XIII) can be obtained by reaction of compounds of General formula (XIV)

R Ar with a salt of hydroxylamine such as hydroxylamine hydrochloride in a solvent such as ethanol or acetonitrile, optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate.

Compounds of General formula (VIII), (IX), (X), (XI), (XII) and (XIV) can be obtained by application or adaptation of known methods.

Skilled in the art, it is known that some compounds of General formula (I) can be obtained by the mutual transformation of other compounds of General formula (I) and such mutual transformations are other features of the invention. Examples of such mutual transformations are described below.

Compounds in which R represents cyano group, can be obtained from compounds in which R represents an ester group CO2R3where R3as defined above, via hydrolysis to the corresponding carboxylic acid by conversion into the corresponding acid chloride by reaction with, for example, thionyl chloride, by treatment with ammonia to floor the defaults group-SOR4or-SO2R4can be obtained by oxidation of compounds in which R2represents a group-SR4using, for example, 3-chloroperbenzoic acid in an inert solvent such as dichloromethane at a temperature from -40 to 0aboutC.

The following examples illustrate the formation of compounds of General formula (I). Unless stated otherwise, percentages are given in mass units.

P R I m e R 1.

Sodium acetate (7.4 g) is added to a mixture of hydroxylamine hydrochloride (6.3 g) and 3-cyclopropyl-2-ethoxymethylene-1-(2-fluorescent-4-IU - tranformer)-propane-1,3-dione (29.0 g) in ethanol. The mixture is stirred at room temperature overnight. The solvent is evaporated and the residue is divided between ethyl acetate and water. The organic phase is washed with water, dried (anhydrous magnesium sulfate), filtered and evaporated to dryness. The residue is ground to powder with ether and filtered. The obtained solid substance will recrystallized from methanol. The mother liquor from the recrystallization are combined and evaporated to dryness. The residue is purified column chromatography on silica gel to obtain 4-cyclopropanecarbonyl-5-(2-fluorescent-4-methylsulfinylphenyl)-isoxazol (compound I) in a solid white of Svetlichny the following connections (see table.2)

P R I m m e R 2. A mixture of 1-[2-chloro-4-(methylsulfinyl)phenyl]-3-cyclopropyl-1 - in-3-one (1.39 g) and atilano-acetimidate (0.8 g) in toluene is stirred and heated at the reflux overnight, cooled and evaporated to dryness. The residue is purified by chromatography by elution with a mixture of hexane and dichloromethane, and then with ether to obtain ethyl-5-[2-chloro-4-(methylsulfinyl)phenyl] -4-cyclopropanecarbonitrile-3-ka rboc(connection 9, to 0.72 g) as a solid orange color, so pl. 50aboutC.

Thus were obtained the following compounds of the appropriately substituted starting materials (see tab.3).

P R I m e R 3. A mixture of 5-[3-chloro-4-(methylsulfinyl)phenyl]-4-cyclopropanecarbonyl-isoxazol (1.0 g) and 3-chloroperoxybenzoic acid (2.3 g, 50% ) in dichloromethane is stirred overnight. Add a saturated solution of sodium bisulfate and the layers separated. The organic phase with sodium bicarbonate solution, water, dried (MgSO4) and filtered. The filtrate is evaporated to dryness to obtain 4-cyclopropanecarbonyl-5-[3-chloro-4-(methylsulphonyl)phenyl] isoxazol (compound 5, 1,11 g) in the form of a substance is white, so pl. 148-150aboutC. in the same manner there were obtained the following compounds from the target hydroxylamine hydrochloride (0.9 g) and 3-cyclopropyl-2-(N, N-dimethylaminomethylene)-1-[5-(metralha-nil) -pyrid-2-yl]propane-1,3-dione (3,24 g) in ethanol. The mixture is stirred for 1 h, then cooled and filtered. The solid is washed with cold ethanol and the filtrate is partially evaporated. Water is added and the mixture was stirred at 0aboutWith 0.5 hours It is extracted with dichloromethane, washed with water, dried (NaSO4) and filtered. The filtrate is evaporated to dryness and the residue purified by chromatography with elution with a mixture of ethyl acetate and hexane to obtain 4-cyclopropanecarbonyl-5-[5-(methylsulfanyl)pyrid-2-yl]isoxazol (compound 13, 0,41 g) as a solid white color, so pl. 103-104aboutC.

Referential example 1. A mixture of 3-cyclopropyl-1-(2-fluorescent-4-methylsulfinylphenyl)-Pro - pan-1,3-dione (7,4 g), triethylorthoformate (8.5 g) and acetic anhydride is stirred and heated under reflux for 4 hours the Mixture is evaporated to dryness. Add xylan and the mixture is again evaporated to obtain 3-cyclopropyl-2-ethoxymethylene-1-(2-fluorescent-4-methylsulfinylphenyl)-propane-1,3-dione (8.8 g) in the form of oil red, which was not cleared.

In this way there were obtained the following compounds of the appropriately substituted starting materials:

R1(R2)nsilecky example 2. A mixture of t-butyl-3-cyclopropyl-2-(2-fluorescent-4-methylsulphonyl- -benzoyl)-3-oxopropionate (10.5 g) and p-toluenesulfonic acid (2.0 g) in toluene is stirred and heated under reflux for 4 hours the Mixture is washed with water, dried (anhydrous magnesium sulfate) and filtered. The filtrate is evaporated to dryness to obtain 3-cyclopropyl-1-(2-fluorescent-4-methylsulfinylphenyl)-propane-1,3-dione (7,4 g) in water resin red,

NMR (DCl3): 0,9-1,3 (m, 4H), 1,8-2,1 (m, 1H), 3,1 (s, 3H), and 6.3 (s, 1H), 7,5-8,0 (m, 3H).

In the same way 3-cyclopropyl-1-(3,4-dichlorophenyl)-propane-1,3-dione was obtained from the appropriately substituted starting material.

Reference example 3. A mixture of magnesium (0.7 g) and t-butyl 3-cyclopropyl-3-oxopropionate (equal to 4.97 g) in methanol is stirred and added carbon tetrachloride (1 ml). The mixture is stirred for 1 h and evaporated to dryness. Add toluene and the mixture is again evaporated to dryness. The residue is dissolved in acetonitrile and added dropwise 2-fluorescent-4-methylsulfonylbenzoyl - chloride (6.5 g). The mixture is stirred 4 h, evaporated to dryness and dissolved in ethyl acetate, washed with diluted hydrochloric acid, dried (anhydrous magnesium sulfate) and filtered. The filtrate is evaporated to dryness to obtain t-butyl-3-cyclopropyl-(2-FPO is one the same way (with the replacement of acetonitrile toluene as reaction solvent) from the appropriately substituted starting material was obtained 3-cyclopropyl-(3,4-dichlorobenzoyl)-3-oxopropionate.

Reference example 4. A mixture of 2-fluorescent-4-methylsulfonylbenzoyl acid (6.0 g) and thionyl chloride is stirred and heated under reflux for 2 hours the Mixture is cooled and evaporated to dryness. Add toluene and the solvent again evaporated to obtain 2-fluorescent-4-methylsulfonylbenzoyl (6.5 g) as a solid brown color, which has not been further purified.

Reference example 5. 2-fluorescent-4-methylsulfinyl)-toluene (25.4 g) is suspended in water and the suspension is heated to 100aboutC. potassium Permanganate (110,2 g) added with such a rate as to maintain a temperature of about 100aboutC. the resulting suspension is filtered and the solid is washed with hot water. The cooled filtrate is extracted with ethyl acetate. The aqueous layer was oxidized to pH 1 and extracted with ethyl acetate. The organic phase is dried (anhydrous magnesium sulfate) and filtered. The filtrate is evaporated to dryness to obtain 2-fluorescent-4-methylsulfonylbenzoyl acid (15.9 g) as a solid orange color, so pl. 187-188aboutC.

Reference example 6. A mixture of 3-fluorescent-4-methylaniline (25 g), dimethyl disulfide (375 g) and t-butyl nitrite (30 ml) in 1,2-dichloroethane warm up before the start of the reaction. A solution of 3-fluorescent-4-methylaniline (225 g) 1 is the temperature below 60aboutC. the Mixture is stirred for 2 h, then add water. The organic layer is washed with water, hydrochloric acid, dried (anhydrous magnesium sulfate) and filtered. The filtrate is evaporated to dryness and the residue is subjected to distillation to obtain 2-fluorescent-4-(methylsulfanyl)-toluene (164 g) as a yellow oil, NMR (acetone-d6), 2,2(3H, d), 2,5(3H, c), 7,05(3H, m).

Reference example 7. A mixture of 3-cyclopropyl-1-[5-(methylsulfanyl)-pyrid-2-yl] propane-1,3-dione (2.9 g), dimethylformamide of dimethylacetate and dioxane was stirred at room temperature overnight. It is evaporated to dryness and the residue is ground to powder with ether and filtered to obtain 3-cyclopropyl-2-(N, N-dimethylaminomethylene)-1.5 to(methylsulfanyl)-PI - Reid-2-yl-propane-1,3-dione (3,24 g) as a solid brown color, which is used without further characterization.

Reference example 8. Cyclopropylmethyl (0.84 g) are added to a suspension of sodium hydride (80% 0.3 g) in dioxane. The mixture is stirred for 20 min and add 1.0 g of ethyl 4-[methylsulfonyl(benzoate). The mixture is stirred and heated at 45aboutWith 1.5 h and at 60about2 h, stand at room temperature overnight. Add hydrochloric acid (2M) and the mixture extracted with ethylacetamide with elution with a mixture of ethyl acetate and hexane to obtain 3-cyclopropyl-1-[4-(methylsulfinyl)-phenyl]-propane)-1,3-dione (0,59 g) as a solid orange color, NMR (CDCl3): 1,0(m, 2H), 1,2(m, 2H), 1.8 m(m, 1H), 2,5(s, 3H), 76,25 (s, 1H), 7,25(d, 2H), 16,35(Shir.s, 1H).

Using the same method the following compounds were obtained from the appropriately substituted starting materials using the above solvent for the reaction (see table.5).

Reference example 9. A solution of 2-(phenylsulfanyl)-4-triftorperasin acid (11.5 g) and thionyl chloride (11.4 g) in dichloromethane containing a few drops of DMF, and heated under reflux for 2 hours the Mixture is evaporated to dryness and add methanol. The mixture is heated under reflux for 1 h and evaporated to dryness. It is treated with water and extracted with ether, washed with sodium carbonate solution (2M), water, dried (Na2SO4) and filtered. The filtrate is evaporated to dryness and the residue is ground to powder with cyclohexane and filtered to obtain methyl 2-(phenylsulfanyl)-4-triftoratsetata (10.5 g) as a solid white color, so pl. 55-60aboutC.

Reference example 10. A mixture of 2-(phenylsulfanyl)-4-triftormetilfosfinov (90 g) in sulfuric acid (50%) is stirred and heated under reflux for 10 hours After cooling it is diluted with water and extracted with DHM. The organic layer extra) and filtered. The filtrate is evaporated to dryness to obtain 2-(phenyl-sulfenyl)-4-triftorperasin acid (75 g) in a solid yellow color, so pl. 161-164aboutC.

Reference example 11. A mixture of 2-nitro-4-triftormetilfosfinov (8,63 g), thiophenol (4.4 g) and potassium carbonate (6.9 g) in acetonitrile is stirred at room temperature for 1 h, then heated under reflux for 9 hours Add thiophenol (0.3 ml) and the mixture is stirred and heated under reflux for 1 h, water is Added and the mixture is extracted with dichloromethane, dried (MgSO4) and filtered. The filtrate is evaporated to dryness and the residue will recrystallized from n-hexane to obtain 2-(peninsul - phenyl)-4-triftormetilfosfinov (9.5 g) as a solid white color, so pl. 51aboutC.

Referential example 12. A solution of n-utility in hexane (4.4 ml) is added to the mixed solution of 2-chloro-4-(methylsulfinyl) phenyl acetylene (2.0 g) in THF while maintaining the temperature below -70aboutC. the Mixture is stirred for 5 min and add cyclopropane - carbonylchloride (2.4 g). The mixture is heated to room temperature and poured on an aqueous solution of sodium chloride. The aqueous layer was extracted with ether and combined organic layers dried is passed fridge 5 minutes Add toluene and the mixture is evaporated to dryness. The residue is purified by chromatography with elution with a mixture of hexane and ether to obtain 1-[2-chloro-4-(methylsulfinyl)phenyl]-3-cyclo - paperpro-1-in-3-it is in the form of a yellow oil, which crystallized upon standing, so pl. 46-50aboutC. 2-Chloro-4-(methylsulfinyl)phenyl acetylene was obtained by the reaction of 1-bromo-2-[2-chloro-4-(methylsulfanyl)phenyl] acetylene with n-butyllithium and wet zinc chloride in THF at -70aboutC.

Reference example 13. n-Utility (2.5 M, 1,45 ml) is added to a stirred cold solution of 1-bromo-2-2-(methylsulfanyl)-4-triptoreline acetylene and 1,1-dibromo-2-2-(methylsulfanyl)-4-Cryptor - were ethylene (1.0 g) in THF maintaining the temperature below -70aboutC. the Mixture is stirred for 30 min and add the chloride cyclopropanecarbonyl (0.75 g). When the temperature reaches room temperature, the mixture is stirred for 2 hours Add aqueous ammonium chloride and the mixture is extracted with ether, dried and filtered. The filtrate is evaporated to dryness and the residue purified by chromatography with elution with a mixture of hexane and ether to obtain 3-cyclopropyl-1-[2-(methylsulfanyl)-4-trifluoromethyl - phenyl] -prop-1-in-3-one (0.64 g) as a yellow oil.

NMR (CDCl3): to 1.15(m, 2H), 1,45(m, nitromethylbenzylidene, 40% in methanol, 1.8 g) in toluene are added to a solution of 1,1-dibromo-2-[2-chloro-4-(methylsulfanyl)Fe - Neil]ethylene (0.96 g) in toluene. The mixture is stirred for 15 minutes Add sulfuric acid (2 M) and the resulting layers separated. The organic layer is washed with water, dried (MgSO4) and filtered. The filtrate is evaporated to dryness and the residue purified by chromatography with elution with a mixture of hexane and dichloromethane to yield 1-bromo-2-[2-chloro-4-(methylsulfanyl)phenyl]acetylene (90,78 g) as a yellow oil.

NMR (CDCl3): of 2.5(s, 3H), 7,05 (d, 1H), and 7.3(s, 1H), 7,35(d, 1H).

Using the same method it was obtained the following compound from the appropriately substituted starting material: 1-bromo-2-[2-(methylsulfanyl)-4-triptime - terphenyl] acetylene in a mixture containing neproreagirovavshimi 1,1-dibromo-2-[methylsulfonyl-4-triptoreline] ethylene.

Reference example 15. Triphenylphosphine (2.5 g) is added to a mixed solution of tetrabromomethane with maintaining the temperature at 0aboutC. the Mixture is stirred for 0.5 h and add 2-chloro-4-(sulfenyl-benzaldehyde) (1.0 g). The mixture is stirred for 0.5 h and poured into hexane. The obtained solid is filtered off and washed with ether. The combined filtrates evaporated to shonil)phenyl] -ethylene (0.96 g) as a solid white color.

NMR (CDCl3): of 2.45(s, 3H), 7,15(d, 1H), 7,25(s, 1H), 7,55 (s, 1H), and 7.6(d, 1H).

In the same way from the appropriately substituted starting material was obtained the following compound: 1,1-dibromo-2-[2-(methylsulfanyl)-4-triptime - terphenyl]ethylene in a solid white color.

NMR (CDCl3): of 2.5(s, 3H), of 7.4 to 7.7(m, 4H).

Reference example 16. A mixture of 2-chloro-4-(methylsulfonyl)-benzoyl chloride (1.0 g) triphenyl of phosphine (2,47 g) and bis(triphenylphosphine)copper (I) borohydride (1.0 g) in acetone was stirred at 0aboutWith 1 hour Then add bis(triphenylphosphine)copper (I) borohydride (1.5 g) and the mixture is stirred for 2 hours the Mixture is filtered and the filtrate evaporated to dryness. The residue is dissolved in chloroform and treated with copper bromide (I) (2.1 g). The filtrate is evaporated to dryness and the filtrate is purified by chromatography with elution with a mixture of ethyl acetate and hexane to obtain 2-chloro-4-(methylsulfanyl)-benzaldehyde (0,83 g) as a solid white color, so pl. 76-77aboutC.

In the same way there was obtained 2-(methylsulfanyl)-4-cryptomaterial guide from a suitable source material.

Reference material 17. n-Utility (2.5 M in hexane, 25 ml) is added under inert atmosphere to a stirred solution of 4-elewaut solid pellets of carbon dioxide, stirred for 10 min and add aqueous hydrochloric acid. The layers are separated and the aqueous layer was extracted with ether. The combined organic layers washed with water, dried (MgSO4) and filtered. The filtrate is evaporated and the residue is ground to powder with cyclohexane and filtered to obtain 2-(methylsulfanyl)-4-triftorperasin acid (12.4 g) as a solid white color.

NMR (CDCl3+DMSO-d6): of 2.45(s, 3H), 7,2(d, 1H), and 7.3(s, 1H), 8.0 a(d, 1H), 10,7-11(Shir.s, 1H).

Reference example 18. t-Butylnitrite (3 ml) is added to a mixture of 3-amino-4-bromobenzonitrile (4 g) and dimethyl disulfide (15 ml) in chloroform. The mixture warm until the beginning of the reaction, when simultaneously add t-butylnitrite (11 ml) and a solution of 3-amino-4-bromobenzonitrile (16 g) in chloroform. The resulting mixture was stirred for 24 h, washed with water, hydrochloric acid (2 M), water, dried (MgSO4) and filtered. The filtrate is evaporated to dryness and the residue is subjected to distillation to obtain 4-bromo-3-(methylsulfanyl)-benzotrifluoride (16.4 g) as a yellow oil, so Kip. 84-88aboutWith 2 mm RT.article.

In accordance with the characteristic of the invention proposes a method of preventing growth of weeds (i.e. undesired vegetation) at the hearth,'s 5-aryl-isoxazol of General formula (I). For this purpose derivatives of 5-aryl isoxazol usually used in the form of herbicide compositions (i.e., together with compatible diluents or carriers and/or surface-active agents suitable for use in herbicide compositions).

Compounds of General formula (I) demonstrate herbicide activity against monocotyledonous and dicotyledonous (i.e., broadleaf) and monocots (i.e., grass) weeds application before or after germination.

The term "application to germination" refers to the application in the soil in which the seeds or sprouts of weeds present before the emergence of weeds on the soil surface. The term "application after germination" refers to the application of the open parts of the weeds that have emerged above the soil surface. For example, compounds of General formula (I) can be used to combat the growth of broadleaf weeds such as Abutilon theophrasti, Amaranthus vetroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Iponoea spp, e.g. Ipomoea purpurea, Sesbania exaltata, Sipapis arvensis, Solanum nigrum and Xanthium strumarium, and grass weeds, for example, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crusgalli, Eleusine indica and Setaria faberii or Setaria viridis and sedges, for example, Cuperus esculentus.

The amount used of the compounds of General formula (I) depends on the nature , to combat weed growth on the area of cultivation of cultures. When used on the area of cultivation, the application rate should be sufficient to control growth of weeds, but should not harm the crop. With these factors in mind the norms of application of between 0.01 kg and 5 kg of active material per hectare give good results. However, you should realize that I can use a higher or lower rate of application depending on the specific task of weed control.

Compounds of General formula (I) can be used for selective control of the growth of weeds, for example to control the growth of those species that were previously mentioned application before or after germination directly or indirectly, as, for example, direct or indirect spray of infectious weeds, which is used for growing crops, such as cereals: wheat, barley, oats, maize and rice, soybeans, field and dwarf beans, peas, alfalfa, cotton, ground nut, flax, onions, carrots, cabbage, radish, sunflower, sugar beet and permanent or cultural pastures before or after sowing of the crop or before or after germination of culture. For selective weed control in the hearth, designed or used for viruses between 0.01 and 2.0 kg of active material per hectare.

Compounds of General formula (I) can also be used to control the growth of weeds, in particular, mentioned above, use before or after germination in groves and other derevorezhushego areas, for example forests, and plantations, for example, sugar cane, maslyanichnoy palm and rubber plantations. For this purpose they can be used directly or indirectly/directly or indirectly sprayed on the weeds or to the soil in which they are located before or after planting of trees or plantations with application rates between 0.25 and 5.0 kg, and preferably between 0.5 and 4.0 kg of active material per hectare.

Compounds of General formula (I) can also be used to control weeds in the pockets of non-land for growing crops, but in which weed control is desired.

Examples of such foci are airports, industrial areas, Railways, roadsides, river banks, irrigation and other channels, shrubs, wastelands and cultivated land, particularly where it is necessary to reduce the risk of fires. When used for such purposes, when often requires a complete herbicide effect, the active compounds are used in higher dosages and accurate dozer is it and it is better to germination direct or indirect spray at application rates between 1,0 and 20.0 kg, and preferably between 5.0 and 10.0 kg of active material per hectare are particularly acceptable for this purpose.

When used to combat weed growth before germination compounds of General formula (I) can be introduced into the soil in which it is assumed the appearance of weeds. When the compounds of formula (I) are used after germination, they come into contact with soil and may then control the germination of weeds, germinating later. If necessary, a longer control application can be repeated.

In accordance with another characteristic of the invention provides a composition suitable for herbicide use, including one or more derivatives of 5-aryl-isoxazol of General formula (I) together with one or more compatible agricultural acceptable diluents or carriers and/or surfactants, and better homogeneity dispergirovannykh in these media, i.e. diluents or carriers and/or surfactants of the type known in the art and suitable for use in herbicide compounds and compositions, and are compatible with compounds of General formula (I). The term "homage the s in other components. The term "herbicide composition is used in a broad sense to include not only compositions which are ready for use as herbicides, but also concentrates that must be diluted before use. Preferably the compositions contain from 0.05 to 90 wt. one or more compounds of General formula (I).

Herbicide compositions may contain a diluent or carrier, and surfactants (e.g., wetting, dispersing or emulsifying substance or agent), a surfactant, present in the herbicide compositions of the invention may be ionic or non-ionic types, for example, sulfonylureas, derivatives of Quaternary ammonium, products based on condensates of ethylene oxide with alkylamine or Polyarylamide phenols, for example, nonyl or octyl-phenols or esters of anhydromannitol carboxylic acids, which are made soluble by etherification of the free gitoxigenin groups by condensation with ethylene oxide, salts of alkaline and alkaline-earth metals esters of sulphuric acid and sulphonic acids, such as of dinonyl and dictinary sulphosuccinate and salts of alkaline and alkaline-earth metal derivatives of sulfonic acids of high molecular mass, such as lignosulfonate invention can include up to 10 wt. for example from 0.05 to 10 wt. Surfactants, but, if desired, even higher proportions of surfactants, for example up to 15 wt. in concentrates liquid emulsion suspension and up to 25 wt. in liquid water soluble concentrates.

Examples of suitable solid diluents or carriers aluminum silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent black coal and clay, such as kaolin and bentonite. The solid compositions (which have the form of dusts, granules or wettable powders) are prepared by grinding the compounds of General formula (I) with solid diluents or by saturation of the solid diluents or carriers with solutions of compounds of General formula (I) in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders. Granular formations can be prepared by absorption of the compounds of General formula (I), dissolved in suitable solvents, which, if desired, can be volatile, solid diluents or carriers in granular form and, if desired, by evaporation of the solvents, or by granulating compositions in powder form obtained as described above. Solid herbicide compositions, especially spaceport to serve as diluents or solvents.

Liquid components according to the invention can take the form of aqueous, organic or vaderlandsch solutions, suspensions and emulsions, which include surfactants. Acceptable liquid diluents for inclusion in the liquid composition, water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylan, ore, animal and vegetable fats and light aromatic and naphthenic oils and mixtures of these diluents. Surfactants in the liquid compositions can be ionic and non-ionic, for example, of the types described above, and in the liquid state can also serve as diluents or carriers.

Powders, dispersible granules and liquid compositions in the form of concentrates can be diluted with water or other suitable diluents, for example, mineral or vegetable oils, especially if in liquid concentrates diluent or carrier is an oil.

If desired, liquid compositions can be used in the form of a self emulsifiable concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of water to such concentrates d is t be used without further dilution by using the technique of electrostatic spraying.

Herbicide composition according to the invention may also include, if desired, conventional drugs that enhance the action (such as adhesives, protective colloids, thickeners, penetrating agents, stabilizers, passivator, antiscale agents and corrosion inhibitors). These drugs may also serve as carriers or diluents.

Unless otherwise specified, the following percentages are given by weight. Preferred herbicide compositions according to the invention are aqueous suspension concentrates comprising from 10 to 70% of one or more compounds of General formula (I), from 2 to 10% surfactant, from 0.1 to 5% of thickener and from 15 to 87.9% water;

wettable powders comprising from 10 to 90% of one or more compounds of General formula (I), from 2 to 10% surfactant, and from 8 to 88% of solid diluent or carrier;

water-soluble or water-dispersible powders comprising from 10 to 90% of one or more compounds of General formula (I), from 2 to 40% of sodium carbonate and from 0 to 88% of solid diluent;

liquid water soluble concentrates comprising from 5 to 50%, for example 10-30% of one or more compounds of General formula (I), from 5 to 25% surfactant and from 25 to 90% for example 45-85% water-soluble solvent, such as dimethylformamide or mixtures% of one or more compounds of General formula (I), from 5 to 15% of surfactants, from 0.1 to 5% of thickener and from 10 to 84,9% of organic solvent;

granules comprising from 1 to 90% for example 2 to 10% of one or more compounds of General formula (I), from 0.5 to 7%, for example 0.5 to 2% surfactant and from 3 up to 98.5% for example 88-97,55% granular media;

emulsion concentrates, comprising 0.05 to 90% and preferably from 1 to 60% of one or more compounds of General formula (I), from 0.01 to 10% and preferably from 1 to 10% surfactant and from 9.99 to 99,94% and preferably from 39 to 98,99% organic solvent.

Herbicide compounds according to the invention may also contain compounds of General formula (I) together with one or more other pesticide active compounds or dispergirujutsja in them, in addition, one or more compatible pesticide acceptable diluents or carriers, surfactants, and drugs that enhance the action. The other examples included in the song data pesticide active compounds include herbicides, for example, increasing the range of weed species: 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-were)-N, N-dimethylation] cyanazine [2-chloro-4-(1-cyano-1-mntla acid] giventhat [1,2-dimethyl-3,5-diphenyl-pyrazoline salt] lampropeltis [methyl-N-(2-N-benzoyl-3-chloro-4-foranyone)- Pro - piont] fermeture [N'-(3-triflora-were)-N, N-demethylation] Isoproturon [N'-(4-isopropylphenyl)-N,N-dimethylation] insecticides such as synthetic pyrethroids, permethrin and cypermethrin and fungicides, for example, carbamates, methyl - N-(1-butyl-carbarnoyl-benzimidazole-2-yl)- carbamate, and triazoles, such as 1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazole-1-yl)- butane-2-on.

Pesticide active compounds and other biologically active materials, which may include or be used together with the compounds of the present invention and which are acid, if desired, can be applied in the form of ordinary derivatives, such as salts of alkali metals and amines, and esters.

In accordance with another characteristic of the invention offers a product that includes at least it is derivative of 5-aryl-isoxazol of General formula (I), or herbicide composition described above, and preferably herbicide concentrate that should be diluted before use, comprising at least one of the derivatives of 5-aryl-isoxazol of General formula (I) inside a container, and instructions to this container outlining the method of use of the specified derivative or herbicide composition contained within to combat weed growth is at normal ambient temperatures and herbicide compositions in particular, in the form of concentrates, such as metal cans, barrels, of which the inside can be covered with a varnish, or made of plastic, bottles of plastic or glass, and if the contents of the container solid material, such as granular, it can be cardboard boxes, plastic and metal or bags. The containers are usually of sufficient capacity to contain a sufficient amount of herbicide for processing at least one acre of land, but does not exceed the size, easy to handle. Instructions must be physically associated with the container, for example printed on it or a special sticker or label attached to the container. There is usually indicated contents of the container, which, after dilution if necessary, is used to combat weed growth with the rate of application is between 0.01 and 20 kg of active material per hectare in a certain way.

The following examples illustrate herbicide compositions in accordance with the invention.

P R I m e R C1. Soluble concentrate is formed from

Active ingredient (compound 1) 20 wt./about

33 wt./about solution of potassium hydroxide 10.about

Tetrahydrofuro - delovogo alcohol (TGFS) 10.about Water To 100 and potassium hydroxide to achieve a constant pH 7-8, and then increase to the desired volume with water.

These soluble concentrates can be prepared as described above by replacing isoxazol (compounds I) to other compounds of General formula (I).

P R I m e R S-2. Wettable powder is formed from the

Active ingredient (compound (I) 50 wt./weight.

Sodium dodecylbenzene sulfonate 3 wt./weight of sodium Lignosulphonate 5 wt. /weight

Sodium formaldehyde

alkylnaphthalene sulfo - Nata 2 wt./weight

Crushed silicon dioxide 3 wt./the weight of China clay 37 wt./weight by mixing the above ingredients together and grinding the mixture in a jet mill.

Similar wettable powders may be prepared as described above by replacing isoxazol (compounds I) to other compounds of General formula (I).

P R I m e R C3.

Water-soluble powder is formed from the

Active ingredi - enta (compound I) 50 wt./weight

Sodium modellbahn - solarvent 1 wt./weight

Crushed silica-2 wt./weight of sodium Bicarbonate 47 wt./weight by mixing the above ingredients and grinding the above-mentioned mixture in a hammer mill.

Such water-soluble powders can PI> The presented compounds of the invention were used in herbicide applications in accordance with the following procedures.

The method of use of herbicide compounds.

a) General part.

The appropriate number of compounds used for treatment of plants, was dissolved in acetone to obtain solutions equivalent to application rates of up to 4000 g of the test compound per hectare (g/ha). These solutions were fed standard laboratory dispenser with a supply of 290 liters of spray fluid per hectare.

b) weed Control: to germination.

Seeds were sown in square plastic pots with a size of 70 mm and a depth of 75 mm in non-sterile soil. The number of seeds per pot following:

1) Broadleaf Approximately

weeds the number of seeds/pot

Abutilon theophrasti 10

Amaranthus retroflexus 20

Galium aparine 10

Ipomoea purpurea 10

Sinapis arvensis 15

Xanthium strumarium 2

2) Grassy weeds

Alopecurus myosuroides 15

Avena fatua 10

Echinochloa crus-galli 15

Setaria viridis 20

3) Sedge

Cyperus esculentus 3

Culture

1) Broad-leaved

Cotton 3

Soy 3

2) Grass

Corn 2

Figure 6

Wheat 6

Prednazanacheny and each weed were subjected to each treatment, control pots were not exposed to the spray, and other control were sprayed only with acetone.

After treatment, the pots were placed on capillary Mat in a greenhouse and watered from above. Visual damage assessment culture was done after 20-24 days after spraying. The results were expressed in percentage growth or damage crops or weeds than plants in the control pots.

(C) Control of weeds after germination.

Weeds and crops were sown directly into compost for pots depth 75 mm, 70 mm square shape. Then the plants were grown in the greenhouse until ready to spray the connections used for the processing plants. The number of plants per pot was as follows:

1) Broad-leaved weeds:

Species Number of plants stage

weeds per pot growth

Abutilon theophrasti 3 1-2 sheet

Amaranthus retroflexus 4 1-2 sheet

Galium aparine 3 1-I mutow-

CA

Ipomoea purpurea 3 1-2 sheet

Sinapis arvensis 4 2 sheets

Xanthium strumarium 1 2-3 leaves

2) Grassy weeds

Species Number of plants stage

weeds per pot growth

Alopecurus

myosuroides 8-12 1-2 sheet

Avena fatua 12-18 1-2 sheet

Echinochloa

Cuperus esculentus 3 3 sheet

1) Broad-leaved

Culture the Number of plants stage

on the potty growth

Cotton 2 1 sheet

Soy 2 2 sheet

2) Grass

Culture

Corn 2 2-3 leaves

Figure 4 2-3 leaves

Wheat 5 2-3 leaves

The connection used for the processing plants, were applied to the plants as described in (a). Each pot of every culture and species of weeds were subjected to each treatment, control pots were not exposed to the spray, and other control pots were sprayed only with acetone.

After treatment, the pots were placed on capillary Mat in a greenhouse and watered from above once after 24 h and then controlled irrigation. Visual assessment of crop damage and weed control was done through 20-24 days after spraying, the results were expressed in percentage growth or damage crops or weeds than plants in the control pots.

Compounds of the invention used with a dosage of 4 kg/ha or less, showed a great level of herbicide activity together with the tolerance of crops to weeds used in the preceding experiments.

When applied to shogenji after germination with a dosage of 1000 g/ha gave a height reduction of 90% of one or more weed species with selectivity in at least one form of culture.

1. Derivatives of 5-arylisoxazoles General formula I

< / BR>
where R is hydrogen or CO2R4;

R1cyclopropyl;

Ar is phenyl or pyridyl, possibly substituted by 1 to 3 groups of R2which may be the same or different;

R2group selected from halogen, R4C1-C4-haloalkyl, -S(O)mR4or-S(O)mR5;

R4- C1-C4-alkyl;

R5phenyl;

m is 0, 1 or 2.

2. Connection on p. 1, where Ar is phenyl, substituted by one or two groups selected from halogen, R4, -S(O)mR4or-S(O)mR5; or Ar is pyridyl, substituted S(O)mR4.

3. Connection PP.1 and 2, which represent: 4-cyclopropanecarbonyl-5-(2-fluorescent-4-methylsulfinylphenyl) isoxazol, 4-cyclopropanecarbonyl-5- (3,4-dichlorophenyl) isoxazol, 4-cyclopropanecarbonyl - 5-[4-(methylsulfinyl)phenyl] isoxazol, 4-cyclopropanecarbonyl - 5-[3-chloro-4- (methylsulfanyl)phenyl] isoxazol, 4-cyclopropanecarbonyl-5-[3-chloro-4-(methylsulphonyl)phenyl] isoxazol, 4-cyclopropanecarbonyl-5 -[4-(methylsulphonyl)phenyl] isoxazol, 4-cyclopropanecarbonyl-5-[4-(methylsulphonyl)phenyl] isoxazol, 4-cyclopropanecarbonyl - 5-[3-methylsulfinyl)phenyl] isoxazol, ethyl 5-[-(methylsulfanyl)-4-triptoreline] isoxazol-3-carboxylate, 1-methylethyl 4-cyclopropanecarbonyl - 5-[2-(methylsulfanyl)-4 - triptoreline] isoxazol-3-carboxylate, 4-cyclopropanecarbonyl-5 -[2-[phenylsulfonyl)-4-triptoreline]-isoxazol-or 4-cyclopropanecarbonyl-5 -[5-(methylsulfanyl) pyrid-2-yl]isoxazol.

4. The method of obtaining derivatives of 5-allocate formula I on p. 1, where R2group SOR4or SO2R4, characterized in that it involves the oxidation of the corresponding compounds of formula I, where R2- SR4.

5. The method of obtaining derivatives of 5-arylisoxazoles formula I

< / BR>
where R is hydrogen;

Ar and R1have the specified values,

characterized in that the compound of General formula V

< / BR>
where L is leaving group,

subjected to interaction with a salt of hydroxylamine.

6. The method of obtaining derivatives of 5-allocate formula I

< / BR>
where R is different from hydrogen;

Ar and R1defined have the specified values,

characterized in that the salt of the compounds of General formula VIII

< / BR>
subjected to interaction with the compound of the formula

RC(X) NOH,

where X is a halogen;

R is different from hydrogen.

7. Herbicide composition comprising the derivative and target isoxazol supplements is great for the CSOs 5-arylisoxazoles formula I

< / BR>
where R is hydrogen or-CO2R4;

R1cyclopropyl;

Ar is phenyl or pyridyl, possibly substituted by 1 to 3 groups of R2that may be the same or different;

R2group selected from halogen, R4C1-C4-haloalkyl, -S(O)mR4or-S(O)mR5;

R4C1-C4-alkyl;

R5phenyl;

m is 0, 1 or 2,

in combination with an agricultural acceptable diluent, carrier and/or surface-active agent.

8. The composition according to p. 7 in liquid form, characterized in that it contains 0.05 to 25% surfactant.

9. The composition according to p. 7 in the form of an aqueous suspension concentrate, wettable powder, water-soluble and water-dispersible powder, water-soluble liquid concentrate, granular or emulsifiable concentrate.

10. The way to suppress weeds in the locus by insertion into the locus derived isoxazol, characterized in that the quality of the derived isoxazol using 5-arylisoxazoles General formula I

< / BR>
where R is hydrogen or CO2R4;

R1cyclopropyl;

Ar is phenyl or pyridyl, possibly substituted by 1 to 3 groups of R2<>-C4-haloalkyl, -S(O)mR4or-S(O)mR5,

R4-C1-C4-alkyl;

R5phenyl;

m is 0, 1 or 2,

in herbicide-effective amount.

11. The method according to p. 10, where the locus is an area used or intend to use for crops.

 

Same patents:

The invention relates to a series of new derivatives of thiazolidinone and oxazolidinone containing nitroacetanilide group, and to methods of producing these compounds may find use of these compounds as vasodilators, for example, for the treatment and prevention of cardiovascular diseases

The invention relates to new pyridazinyl, derivatives which have the General formula:

(1) where one or two carbon atoms of methylene groups in the residue-NX - can be substituted by alkyl WITH1-C4, alkoxygroup1-C4or two carbon atom of the methylene groups of the above-mentioned residue can be connected by bridge with alkane(C2-C4)delovym radical; X represents CH or a nitrogen atom; each of m and n, independently of one another, denotes 1, 2, 3, and the sum m+n is 3, 4 or 5; R1denotes a hydrogen atom, alkyl WITH1-C4the halogen atom; each of R2and R3independently denotes a hydrogen atom or alkyl WITH1-C4; Аlк denotes alkane(C1-C4)diyl, each of R4and R5independently denotes hydrogen atom or halogen atom, or WITH1-C4-alkyl, and Неt denotes the group of one of formulae

where R6denotes a hydrogen atom, alkyl (C1-C6), oxyalkyl(C1-C6), cycloalkyl(C3-C6), phenyl or amino; each of R7independently denotes a hydrogen atom, alkyl (C1-C6), cycloalkyl(C3-C6), phenyl or trifluoromethyl, and their salts or a stereochemical isomeric form

The invention relates to the production of new proizvodnyh of thiazolidine that are used in pharmaceutical compositions

The invention relates to a new derivative of uracil with herbicide action

The invention relates to new derivatives of 4-benzisoxazole, compositions containing them and their use as herbicides, in particular to derivatives of 4-benzisoxazole General formula [1]

_(I) where R1means a straight or branched alkyl, alkenyl or quinil containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or by a group-СООR5, cyclo-alkenyl containing 5 or 6 carbon atoms, which may be substituted by one or more groups R5one or more halogen atoms or a group COOR5, aryl or aralkyl (e.g., benzyl), General formula [(R2)qphenyl] -[C(R3)(R4)]p(aryl typically contains 6-10, aralkyl 7-11 carbon atoms), an ester group COOR5, aldehyde or acyl group COR3, cyano - or nitro-group, amino group NR3R4or halogen atom (such as F, Cl, Br, J);

R2means nitro - or cyano-group is Il-SO2NR3R4; ester group СOOR5, acyl or aldehyde group,-COR3, carbarnoyl CONR3R4or thiocarbamoyl CSNR3R4alkoxygroup QR5or alkyl containing 1-3 carbon atoms, substituted by a group OR5;

R3and R4may be the same or different and are each a hydrogen atom or a straight or branched alkyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms;

R5straight or branched alkyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms;

R6a hydrogen atom, oxygraph IT, halogen atom, for example, F, Cl, Br, J, R5alkenyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or by a group-СOOR5, sulfenyl, sulfinil or sulfonyl S(O)mR5, ester group COR3, carbamoyl CONR3R4or thiocarbamoyl CSNR3R4group, alkoxygroup-OR5phenoxy> benzyloxy OCO-phenyl-(R2)qgroup special Неt 1, carbamoyloximes OCON R3R4alkylsulfonates OSO2R8peninsul - philokyprou OSO2-phenyl-(R2)qsulfaminokislotu OSO2-NR3R4the amino group NR3R4alluminare NR3COR5or the group Het 2;

R7a hydrogen atom, a group R5or R6and R7together with the carbon atom to which they are bound, form ketal (OR5)2thioketal (SR5)2cyclic ketal or cyclic thioketal containing 5-6 ring atoms, which may be substituted by one or more groups R5;

R8straight or branched alkyl or alkenyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or a group COOR5;

Неt 1 of the heterocycle with 5 or 6 ring atoms, one or more of which are heteroatoms selected from nitrogen atoms, sulfur and oxygen, with the ring carbon atoms may be sameshima, 1,2,4-triazole-1-yl, 1,2,3-triazole-1-yl or 1,2,3-triazole-2-yl, each of which may be substituted by one or more groups R2;

m is 0, 1 or 2;

n 1-5;

q represents 0 or an integer from 1 to 5;

p is 0 or 1, and their acceptable from the point of view of their use in agriculture salts with herbicide activity

The invention relates to new chemical compounds, particularly to derivatives of 1,2-bis-(5-phenyloxazolyl-2)Ben - ash formula I

Rwhere R H (a); C6H5(b); N(CH3)2(c); CH3(d)

The invention relates to synergistic combinations of the known fungicidal active ingredients and their use as plant protection

The invention relates to new derivatives of 4-benzisoxazole, compositions containing them and their use as herbicides, in particular to derivatives of 4-benzisoxazole General formula [1]

_(I) where R1means a straight or branched alkyl, alkenyl or quinil containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or by a group-СООR5, cyclo-alkenyl containing 5 or 6 carbon atoms, which may be substituted by one or more groups R5one or more halogen atoms or a group COOR5, aryl or aralkyl (e.g., benzyl), General formula [(R2)qphenyl] -[C(R3)(R4)]p(aryl typically contains 6-10, aralkyl 7-11 carbon atoms), an ester group COOR5, aldehyde or acyl group COR3, cyano - or nitro-group, amino group NR3R4or halogen atom (such as F, Cl, Br, J);

R2means nitro - or cyano-group is Il-SO2NR3R4; ester group СOOR5, acyl or aldehyde group,-COR3, carbarnoyl CONR3R4or thiocarbamoyl CSNR3R4alkoxygroup QR5or alkyl containing 1-3 carbon atoms, substituted by a group OR5;

R3and R4may be the same or different and are each a hydrogen atom or a straight or branched alkyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms;

R5straight or branched alkyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms;

R6a hydrogen atom, oxygraph IT, halogen atom, for example, F, Cl, Br, J, R5alkenyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or by a group-СOOR5, sulfenyl, sulfinil or sulfonyl S(O)mR5, ester group COR3, carbamoyl CONR3R4or thiocarbamoyl CSNR3R4group, alkoxygroup-OR5phenoxy> benzyloxy OCO-phenyl-(R2)qgroup special Неt 1, carbamoyloximes OCON R3R4alkylsulfonates OSO2R8peninsul - philokyprou OSO2-phenyl-(R2)qsulfaminokislotu OSO2-NR3R4the amino group NR3R4alluminare NR3COR5or the group Het 2;

R7a hydrogen atom, a group R5or R6and R7together with the carbon atom to which they are bound, form ketal (OR5)2thioketal (SR5)2cyclic ketal or cyclic thioketal containing 5-6 ring atoms, which may be substituted by one or more groups R5;

R8straight or branched alkyl or alkenyl containing up to 6 carbon atoms which may be substituted by one or more halogen atoms, cycloalkyl containing 3-6 carbon atoms that may be substituted by one or more groups R5one or more halogen atoms or a group COOR5;

Неt 1 of the heterocycle with 5 or 6 ring atoms, one or more of which are heteroatoms selected from nitrogen atoms, sulfur and oxygen, with the ring carbon atoms may be sameshima, 1,2,4-triazole-1-yl, 1,2,3-triazole-1-yl or 1,2,3-triazole-2-yl, each of which may be substituted by one or more groups R2;

m is 0, 1 or 2;

n 1-5;

q represents 0 or an integer from 1 to 5;

p is 0 or 1, and their acceptable from the point of view of their use in agriculture salts with herbicide activity

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

Control of weeds // 2246828

FIELD: agriculture, plants science.

SUBSTANCE: one should treat the focus in solid medium with a composition containing an isoxasol-based herbicide to provide either gradual or successive supply or release of an isoxasol-based herbicide into surface layer of the medium. As a result, it has been obtained the composition containing an isoxasol-based herbicide being of delayed releasing.

EFFECT: higher efficiency of weeds' control.

10 cl, 5 ex, 1 tbl

FIELD: organic chemistry, agriculture.

SUBSTANCE: substituted benzoylisoxazols of general formula I are described, wherein R1 is cycloalkyl; R2 is hydrogen, alkoxycarbonyl; R3 is halogen, substituted alkyl, alkoxyl; R4 is halogen, alkoxil; Z is substituted 5-membered saturated or unsaturated heterocycle having 1-3 nitrogen atoms and additionally including one oxogroup (C=O). Also disclosed is herbicidal agents, containing compounds of formula I.

EFFECT: effective suppression of weeds in such cultures as maize and wheat.

16 cl, 6 tbl, 4 ex

FIELD: agrochemistry.

SUBSTANCE: invention provides a stable aqueous formulation of hydrophobic pesticide by emulsifying aqueous phase and a water-immiscible phase, the former containing poly(alkylene glycol) ether and the latter hydrophobic pesticide and one or several emulsifiers selected from group including carboxylate, sulfate, sulfonate, alcohol solutions of ethoxylated and alkylphenolethoxylate, fatty acid ethyl ester, sorbitol ester, ethoxylated fat or oil, aminoethoxylate, ethylene oxide/propylene oxide copolymer, fluorocarbon, and siliceous polymer.

EFFECT: increased stability of formulations.

38 cl, 1 tbl, 12 ex

FIELD: medicine.

SUBSTANCE: claimed composition contains 2-methylisotiazolin-3-one as biocide active ingredient and additional biocide active ingredient selected from group containing formaldehyde or compound releasing the same, 2-bromo-2-nitro-1,3-propanediol, polyhexamethylene biguanidine, o-phenylphenol, zinc, iron, copper pyrithione, N-buthyl-1,2-benzoisothiazoline-3-one, N-hydroxymetnyl-1,2-benzoisothiazoline-3-one in 2-methylisotiazolin-3-one/additional biocide active ingredient mass ratio of 1:100-100:1. Application of claimed composition for pestiferous microorganism controlling also is described.

EFFECT: synergic composition effective at low total concentration of biocide ingredients.

16 cl, 18 tbl, 9 ex

Herbicidal agent // 2271659

FIELD: organic chemistry, agriculture, herbicides.

SUBSTANCE: invention relates to herbicidal agent containing compound of general formula I wherein X represents residue X1 or X2 and Z, R1 and R2 are as defined in claim of invention, and additional active substance selected from group containing bromoxynil, dicamba, flufenacete, metolachlor, atrazine, pendimethaline, imazetapir, iodosulfuron, nicosulfuron, 2-amino-4-(1-fluoro-1-methyl)-6-(3-phenyl-1-cyclobuthyl-1-propylamino)-1,3,5-triazine and N-[(4,6-dimethoxy-pyrimidine-2-yl)-aminocarbonyl]-2-dimethylamino-carbonyl-5-formyl-benzenesulfonamide. Compound of formula I and additional active substance are taken in mass ratio of 1:20-10:1, respectively.

EFFECT: agent of high herbicidal activity.

6 cl, 15 ex

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