RU2266904C2 - Sulfonamide derivatives, method for their preparing and method for weed eradication - Google Patents

Abstract

FIELD: organic chemistry, chemical technology, herbicides, agriculture.

SUBSTANCE: invention relates to new sulfonamides of the formula (I):

and their salt wherein A represents substituted or unsubstituted benzene ring or 5-membered, or 6-membered substituted or unsubstituted heteroaromatic ring taken among the group comprising thienyl, pyrazolyl, imidazolyl, pyridyl wherein optional substitutes are taken among the group consisting of halogen atom, substituted or unsubstituted (C₁-C₄)-alkyl, unsubstituted or substituted (C₁-C₄)-alkoxy-group, nitro-group, phenyl, phenoxy-group, benzoyl and (C₁-C₄)-alkylcarboxylate when any alkyl fragment in the latter indicated substituted is substituted with one or some halogen atoms, (C₁-C₄)-alkoxy-groups, cyano-group and phenyl; Q represents -O-, -S- or group of the formula: -CXX' wherein X and X' can be similar or different and each represents hydrogen atom, halogen atom, cyano-group, alkyl comprising 1-8 carbon atoms, or the group -OR^a, -SR^a; or one of X and X' represents hydroxy-group and another has values determine above; R^a means (C₁-C₈)-alkyl, phenyl; R^b means (C₁-C₈)-alkyl, phenyl; Y means nitrogen atom or the group CR⁹; R¹ means unsubstituted (C₁-C₈)-alkyl or that substituted with halogen atom, cyano-group, phenyl or (C₁-C₄)-alkoxycarbonylamino-group, or it represents phenyl; R² means hydrogen atom (H), (C₁-C₄)-alkyl; R³ and R⁴ can be similar or different and each represents (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-group, halogen atom; R⁹ means hydrogen atom (H) under condition that when Q represents oxygen atom (O) or -S- then ring A represents 5-membered substituted or unsubstituted heteroaromatic ring and determined above. Compounds of the formula (I) possess the herbicide activity that allows their using for eradication of weeds. Also, invention describes a method for preparing compounds of the formula (I).

EFFECT: improved preparing method, valuable properties of compounds.

9 cl, 5 tbl, 18 ex

Description

The present invention relates to herbicidal sulfonamides, methods for their preparation and formulations based on them.

Patents EP No. 323040 and WO No. 91/10653 disclose herbicidal sulfonamides related to the compounds of the present invention.

One of the objects of the present invention are new sulfonamides of the formula:

and their salts, where

A represents a substituted or unsubstituted benzene ring, or a 5-membered substituted or unsubstituted heteroaromatic ring;

-Q- represents -O-, -S- or a group-CXX'-,

X and X ', which may be the same or different, represent a hydrogen atom, a halogen atom, a cyano-, possibly substituted alkyl group, or a group —OR ^a , —SR ^a or —COR ^b ; or one of X or X 'represents a hydroxyl group, and the other takes on the meanings defined above; or X and X 'together form a group = O or = S;

R ^a represents a possibly substituted alkyl, aryl or acyl group;

R ^b represents a possibly substituted alkyl or aryl group, or is —OR ^c or —NR ^c R ^d ;

R ^c and R ^d , which may be the same or different, represent a hydrogen atom, an optionally substituted alkyl or aryl group;

Y represents a nitrogen atom or a group CR ⁹ ;

R ¹ represents a possibly substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl group, heterocyclic, benzoheterocyclic or amino group;

R ² represents a hydrogen atom, an optionally substituted alkyl or carboxyl acyl group; or a group —SO ₂ R ¹ ;

R ³ and R ⁴ , which may be the same or different, represent a hydrogen atom, a halogen atom, possibly a substituted alkyl, alkoxy, cycloalkyl or amino group or a possibly substituted heterocyclic group; and

R ⁹ represents a hydrogen atom or possibly a substituted alkyl group;

with the proviso that when Q is —O— or —S—, ring A is a 5-membered substituted or unsubstituted heteroaromatic ring; and

with the proviso that when the substituent R ¹ is substituted alkyl, it is not a group of the formula:

where the substituent X ″ represents an oxygen or sulfur atom, and each of the substituents R ⁶ , R ⁷ and R ⁸ represents a hydrogen atom or possibly a substituted alkyl group.

When A is a 5-membered heterocyclic ring, it preferably is a substituted or unsubstituted thiophene, furan, pyrrole, thiazole, isothiazole, pyrazole, imidazole, oxazole or isoxazole ring.

In ring A, any of the substituents at the carbon atom preferably represents a halogen atom, a cyano group, a —COOR ¹⁰ group (where the substituent R ¹⁰ represents a hydrogen atom or a possibly substituted alkyl group), or a possibly substituted alkyl, alkoxy, aryloxy- heterocyclyloxy or amino group. Preferably, such substituent groups are fluorine and chlorine atoms.

Any of the substituents on the nitrogen atom of ring A is preferably a substituted or unsubstituted alkyl, alkoxy, amino or aryl group, especially a methyl group.

Any of the alkyl groups present in the molecule preferably has from 1 to 8 carbon atoms, more preferably from 1 to 6 carbon atoms, especially from 1 to 4 carbon atoms. Particular preferred unsubstituted alkyl or alkyl-containing groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, methoxy, ethoxy and n-propoxy.

If any of the alkyl groups in the molecule is substituted, then the substituents can be, for example, one or more halogen atoms (e.g. fluorine, chlorine or bromine), alkoxy or alkylthio groups containing from 1 to 4 carbon atoms (e.g. methoxy or ethoxy -), hydroxy, nitro, mercapto, amino, substituted amino groups, carbamoyl, substituted carbamoyl, thiocarbamoyl, substituted thiocarbamoyl, cyano, acyl, aryl or heteroaryl groups. Particularly preferred substituted alkyl-containing groups are chloromethyl, bromomethyl, dichloromethyl, trifluoromethyl, difluoromethoxy, cyanomethyl, methoxyethyl or ethoxyethyl.

Any of the alkenyl or alkynyl groups present in the molecule preferably has from 2 to 6 carbon atoms, for example vinyl, allyl or propargyl. Any such alkenyl or alkynyl group is preferably unsubstituted, although, if necessary, it may be substituted, for example, with halogen.

Any of the cycloalkyl groups present in the molecule preferably has from 3 to 7 carbon atoms, a cyclopentyl or cyclohexyl group is particularly preferred. They are preferably unsubstituted.

Any of the aryl groups present in the molecule is preferably phenyl, which is preferably substituted by one or more alkyl, alkoxy, alkoxycarbonyl or alkylthio groups containing from 1 to 4 carbon atoms (and which in turn may be substituted), halogen atoms, cyano -, aminosulfonyl or nitro groups; it is particularly preferred that the phenyl group is substituted with one or more chlorine, bromine or fluorine atoms, and / or one or more methyl, methoxy, trifluoromethyl, methylthio, methoxycarbonyl, ethoxycarbonyl or nitro groups.

Any of the heterocyclyl groups in the molecule that is not ring A is preferably a furyl, thienyl or nitrogen containing heterocycle, for example a 5- or 6-membered heterocyclic ring, for example pyrrolyl, oxazolyl, isoxazolyl, isothiazolyl, pyrimidinyl, triazolyl or imidazolyl. The substituent R ¹ may also preferably be a pyridyl, furyl, thienyl or bicyclic heterocyclyl group, for example triazolotriazolyl, triazolopyrimidinyl or pyrazolopyrimidinyl.

Any of the benzoheterocyclyl groups in the molecule is preferably a benzothiophene, benzodioxolane, quinoline, quinazoline, benzothiazole or dihydrobenzofuran group.

Any of the halogen atoms in the molecule is preferably a fluorine, chlorine or bromine atom.

Any of the substituted amino groups in the molecule may be mono- or disubstituted, for example, alkyls containing from 1 to 4 carbon atoms, alkenyls containing from 2 to 4 carbon atoms, carbamoyl or acyl carboxyl, alkoxycarbonyl, alkylcarbamoyl or dialkylcarbamoyl groups in which a group contains from 1 to 4 carbon atoms.

The term “acyl” as used herein means a residue of a carboxylic, sulfonic or phosphorus-containing acids, for example, alkanoyl, alkenoyl, alkynoyl, cycloalkanoyl, aralkanoyl, aroyl, carbamoyl, thiocarbamoyl, alkoxycarbonyl, sulfonyl, sulfamoyl and alkylphosphonyl groups or aryl groups may be substituted or unsubstituted.

Particularly preferred groups in which R ¹ may be methyl, chloromethyl, bromomethyl, cyanomethyl, trifluoromethyl or 2,2,2-trifluoroethyl.

The substituent R ^{2 is} preferably a hydrogen atom.

Each of R ³ and R ⁴ preferably represents a hydrogen atom, methyl, methoxy group or a chlorine atom.

It is particularly preferred that the substituents R ³ and R ^{4 are the} same and most preferably both of them are methoxy.

Ring A is preferably benzene (possibly substituted by fluorine, chlorine, bromine, methyl, methoxy or ethoxy groups) or pyrazole (optionally substituted by one or more methyl groups).

The substituent Q is preferably —CH ₂ -, —CH (CH ₃ ) -, —S—, or —O—.

Preferred salts of the compounds of formula I are salts formed with strong bases, such as alkali metal salts (e.g., potassium or sodium), amine salts (e.g., trifthylamine, diisopropylamine, cyclohexylamine or piperidine).

The most preferred compounds of the present invention are compounds which are given in the Examples below.

Another object of the present invention is a method for producing a sulfonamide of formula I, which consists in the interaction of an amine of the formula:

where the substituents A, Q, Y and R ² —R ⁴ are as defined above, with a suitable sulfonic anhydride of the formula (R ¹ SO ₂ ) ₂ O or a sulfonyl halide of the formula R ¹ SO ₂ Hal, where Hal is a halogen atom and the substituent R ¹ takes the above values, with the formation of the desired compound.

The reaction proceeds quite easily in the presence of a base, for example an organic base such as pyridine.

In turn, the compounds of formula II can be obtained by reaction of a substituted amine of the formula:

where A, Q and R ² take the above values, in the presence of a base with a compound of the formula:

where the substituents Y, R ³ and R ⁴ take the values described above, and the substituent L is a leaving group, with the formation of the desired compound.

The leaving group L may be any suitable group for this, but preferably it is a halogen atom, especially a chlorine atom, or a methylsulfonyl group.

Alkyl lithium, for example tert.-butyllithium, is preferably used as the base, and the reaction is preferably carried out in a solvent, for example tetrahydrofuran.

Compounds of formula II in which the substituent R ² represents a hydrogen atom can alternatively be prepared by reduction of the corresponding nitro compounds of the formula:

where the substituents A, Q, Y, R ³ and R ⁴ take the above values.

Recovery is conveniently carried out using tin (II) chloride; an alternative method is to treat iron in an acidic medium, particularly preferably in trifluoroacetic acid and / or its anhydride, by methods that are known per se. According to the latter procedure, the nitro group is initially converted to the —NHCOCF ₃ group, which is then converted to the amino group by the action of a base, such as potassium carbonate.

If necessary, compounds of formula II can be converted into other compounds of formula II by known methods. For example, compounds of formula II in which X or X ′ is an alkyl group can be prepared from the corresponding compounds of formula II in which Q is —CH ₂ - and R ² is a hydrogen atom, initially protecting the amino group, for example reacting the compound with di-tert-butyl dicarbonate, treating the protected compound with an alkylating agent, for example methyl iodide, in the presence of a strong base, followed by deprotecting the amino group, for example, trifluoroacetic acid.

In turn, compounds of formula V can be prepared by reacting a compound of formula:

where substituent A takes the above values, and Hal is a halogen atom, in the presence of a base with a compound according to formula IV, in which the substituents R ³ and R ⁴ are as defined above, and the substituent L is an —OH group, where the substituent Q is the values described above.

Alternatively, compounds of formula V can be prepared by the reaction of a nitro compound of the formula:

where the substituents A and Q take the values described above, and the substituent L represents a leaving group (preferably a chlorine atom or imidazol-I-yl), in the presence of a base with a compound of the formula R ³ C (= NH) YHC (= NH) R ⁴ , where the substituents Y, R ³ and R ⁴ take the above values.

A preferred base is diisopropylethylamine.

Compounds of formula II, wherein substituent A is an N-methylpyrazole ring and substituent R ³ is a hydrogen atom, can alternatively be prepared by reacting dimethylaminoacrylonitrile of the formula:

where the substituents Q, Y, R ³ and R ⁴ take the above values, with methylhydrazine in acetic acid to form the target compound.

The starting materials in the processes described above, in particular especially the compounds of formulas III, IV, VI, VII and VIII, are either known compounds or can be obtained by known methods from related compounds that are well known to those skilled in the art.

Salts of compounds of formula I can be prepared by known methods by treating the corresponding free compounds with a suitable base in a suitable solvent (for example, ether).

Compounds of formula I in which the substituent R ² is other than a hydrogen atom can alternatively be prepared from salts of the compounds of formula I by reaction with a suitable alkylating or acylating agent containing the desired R ² group by methods analogous to known methods.

The compounds of formula I possess herbicidal activity against a wide range of broad-leaved and cereal weeds, but are relatively safe for some crops. Therefore, they can be used as selective herbicides, in particular, for the destruction of a large number of weeds in crops of cereals, sugar beets or other crops, for example wheat, barley, corn, soy, oilseed rape, cotton or rice.

Thus, another object of the present invention is a method of destroying weeds in areas littered with weeds or in areas where they are expected to occur, which consists in processing the above areas with an effective amount of one or more compounds of formula I.

Desirable doses for the use of compounds of formula I or their salts are doses in the range from 0.001 to 2 kg / ha, preferably from 0.005 to 1 kg / ha, more preferably from 0.01 to 0.5 kg / ha.

Another object of the present invention are formulations which contain one or more compounds of the present invention in admixture with an acceptable carrier and / or surfactant.

Formulations typically contain 0.01 to 99 wt.% Of the compounds of the present invention and are usually initially prepared in the form of concentrates containing from 0.5 to 99%, preferably from 0.5 to 85% and more preferably from 10 to 50 wt.% Of these compounds. Such concentrates are diluted, if necessary, before processing the sites so that the content of the active ingredient in the formulation used is from 0.01 to 5 wt.%.

Water may be used as a carrier, in which in some cases an organic solvent may be contained, although it is usually not used. A flowable suspension concentrate can be obtained by grinding the compound with water, a wetting agent and a suspending agent, for example, xanthan gum.

A water-immiscible organic solvent, for example, a hydrocarbon boiling in the range of 130-270 ° C, for example xylene, in which the compound of the present invention is dissolved or suspended, can be used as a carrier. An emulsifiable concentrate can also be obtained containing a water-immiscible solvent and a surfactant such that the concentrate acts as a self-emulsifiable oil when mixed with water.

A solid product can also be used as a carrier, which is subjected to fine grinding or granulation. Examples of suitable solid carriers are limestone, clay, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers. The carrier may be a natural or synthetic material, or a modified natural product.

Wettable powders, soluble or dispersible in water, can also be prepared by mixing the particulate compound of the present invention with a particulate carrier or by spraying the molten compound onto a particulate carrier mixed with a wetting agent and a dispersing agent and then grinding the entire powder mixtures.

An aerosol formulation may be prepared by mixing a compound of the present invention with a propylene, for example polyhalogenated alkanes, such as dichlorofluoromethane, and also, if necessary, with a solvent.

The term "surfactant" in the broad sense includes materials called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.

The surfactants used may be anionic, for example, such as mono- or diesters of phosphoric acid and ethoxylated fatty alcohols, or salts of such esters, sulfates of fatty alcohols, such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkyl phenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates, such as alkylbenzenesulfonates or lower alkylnaphthalenesulfonates, salts of sulfonated condensation products of naphthalene with formaldehyde, or more complex with lfonaty such as amide sulphonates, eg the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulphosuccinates eg the sodium salt of sulfated dioctylsuccinate.

Surfactants can also be nonionic agents, for example, condensation products of either fatty acid esters, fatty alcohols, fatty acid amides, or alkyl substituted phenols with ethylene oxide, fatty acid ethers with polyhydric alcohol ethers, for example sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, for example polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylene glycols such as 2,4,7,9-tetramethyl-5-decin-4,7-d iol, or ethoxylated acetylene glycols.

Surfactants can also be cationic agents, for example, alkyl and / or aryl substituted quaternary ammonium compounds, such as cetyltrimethylammonium bromide, and ethoxylated fatty tertiary amines.

Preferred surfactants are ethoxylated fatty alcohol sulfates, ligninsulfonates, alkylaryl sulfonates, salts of sulfonated naphthalene-formaldehyde condensation products, sodium oleyl-N-methyltauride, dialkyl sulfosuccinates, ethoxylated alkyl phenols and fatty alkyl ethoxylates.

The active compounds of the present invention, especially those presented in the Examples below, can be mixed with other pesticides, for example with another herbicide, fungicide or insecticide or with a plant growth regulator. The use of another herbicide is particularly preferred. Acceptable additional herbicides are trietazine, linuron, MCPA, dichloroprop, isoxaben, difluvenican, metolachlorne, fluoromethuron, oxyfluorfen, fomesafen, bentazone, promethrin, norflurazone, chlomazonofininlazone, moreazinquinolinazole, more preferably mecoprop, fluroxypyr, alachlor, acifluorfen, lactophen, metribuzin and pendimethalin, and most preferably etofumesate and phenmedifam.

The compounds of the present invention can be used to treat plants, soil, land and water, and especially areas where crops grow or where they will be grown. These compounds have both pre-emergence and post-emergence activity.

The invention is illustrated by the following examples.

EXAMPLE A

EXAMPLE A1

1,1,1-Trifluoro-2 '- (4,6-dimethoxypyrimidin-2-ylmethyl) methanesulfonanilide

(a) 2- (4,6-Dimethoxypyrimidin-2-ylmethyl) aniline

Method 1

To a solution of o-toluidine (5.35 g) in dry tetrahydrofuran (100 ml), n-butyllithium (21 ml of a 2.5 M solution in hexane) was added dropwise under stirring at a temperature of -70 ° C. The resulting suspension was allowed to warm to 5 ° C, obtaining a light yellow solution. Dry carbon dioxide was bubbled into the reaction mixture for approximately 6 minutes. The solvent was evaporated with stirring under high vacuum at room temperature. The resulting white solid was suspended in dry tetrahydrofuran and cooled to 70 ° C. under nitrogen and tert.-butyllithium (70 ml of a 1.6 M solution in pentane) was added dropwise over 15 minutes. The mixture was allowed to warm to -15 ° C and stirred at this temperature for 75 minutes. The mixture was cooled to −70 ° C. and a solution of 4,6-dimethoxy-2-methylsulfonylpyrimidine (10.9 g) in tetrahydrofuran was added dropwise. The mixture was stirred at -75 ° C for 60 minutes and left overnight at room temperature. The solvent was evaporated in vacuo, 2N was added to the residue under a nitrogen atmosphere under cooling with ice-water. hydrochloric acid. Then 250 ml of water are added, the resulting turbid solution is alkalinized with saturated sodium bicarbonate solution and extracted with ether (2 × 400 ml). The combined extracts were washed with saturated sodium bicarbonate solution, dried and evaporated. The resulting orange oil is purified by chromatography to give 2 g of the product as a yellow solid, mp. 82-84 ° C.

Method 2

(I) 4,6-Dimethoxy-2- (2-nitrobenzyl) pyrimidine

To a suspension of malonimidate dichlorohydrate (73.2 g) in methylene chloride (400 ml) at -40 ° C under nitrogen atmosphere, diisopropylethylamine (240 ml) is added dropwise with stirring, stirred for 25 minutes to obtain a suspension of A. To a suspension of carbonyldiimidazole (53.3 g) in methylene chloride (400 ml), 2-nitrophenylacetic acid (65.16 g) was added portionwise with stirring at room temperature. The resulting solution was stirred for 10 minutes and was added dropwise to suspension A at -40 ° C over 30 minutes with stirring. The mixture was stirred at -40 ° C for 45 minutes and at room temperature overnight. The solution was washed with water (400 ml), 2 N. HCl (400 ml) and saturated sodium bicarbonate solution (400 ml), dried and evaporated. The resulting orange solid was stirred with 2-propanol (60 ml) for 10 minutes and filtered. The filtrate was washed with 50 ml of 2-propanol and dried, to obtain 32.6 g of the desired product as a yellow solid, so pl. 92-93 ° C.

(II) 2- (4,6-Dimethoxypyrimidin-2-ylmethyl) aniline

To a suspension of tin (II) chloride dihydrate (133 g) in ethanol (300 ml), the product from step (I) is added with stirring. The mixture was boiled for 2 hours, poured into ice water (2500 ml) and extracted with ethyl acetate (3 × 500 ml). The combined extracts were washed with saturated sodium chloride solution, dried and evaporated to give 24.3 g of the desired product as a brown solid, mp. 82-84 ° C.

(b) 1,1,1-Trifluoro-2 '- (4,6-dimethoxypyrimidin-2-ylmethyl) methanesulfonanilide

To a solution of 2- (4,6-dimethoxypyrimidin-2-ylmethyl) aniline (0.98 g) and pyridine (0.31 g) in dry methylene chloride (15 ml) at -70 ° C under nitrogen atmosphere, trifluoromethanesulfonic anhydride (1.12 g) is added in portions. The resulting orange solution was stirred for 2 h at -75 ° C and allowed to warm to room temperature for 1 h. The mixture was washed with water, dried, and a red oil was obtained, which was purified by chromatography and recrystallization from petroleum ether 60-80 °, 0.4 g was obtained product in the form of a white solid, so pl. 99-100 ° C.

EXAMPLE A2

1,1,1-Trifluoro-2 '- [1- (4,6-dimethoxypyrimidin-2-yl) ethyl] methanesulfonanilide

(a) tert.-Butyl- [2- (4,6-dimethoxypyrimidin-2-ylmethyl) phenyl] carbamate

A solution of the product from step (a) of Example A1 (24.1 g) and di-tert-butyl dicarbonate (24 g) is boiled in dry tetrahydrofuran (250 ml) under nitrogen for 4 hours. The solvent is evaporated, the resulting brown oil is crystallized from hexane ( 200 ml), 28 g of the desired compound are obtained in the form of a brown solid, mp. 98-100 ° C.

(b) tert.-Butyl- [2- [1- (4,6-dimethoxypyrimidin-2-yl) ethyl] phenyl] carbamate

The product from the above step (a) (1 g) was dissolved in dry tetrahydrofuran (20 ml) and tetramethylethylenediamine (1.1 ml) was added under nitrogen atmosphere. The solution was cooled to -70 ° C and a 1.7 M solution of tert.-butyllithium in pentane (4.3 ml) was added dropwise. The mixture was then stirred at -20 ° C for 1 h, cooled to -70 ° C and methyl iodide (0.45 g) was added. The reaction mixture was allowed to warm to 0 ° C. and a saturated solution of ammonium chloride (25 ml) was added. The mixture is extracted with tetrahydrofuran (3 × 50 ml), the combined extracts are dried and evaporated, the resulting pale brown solid is triturated with hexane, 0.73 g of the desired product is obtained, so pl. 119-121 ° C.

(c) 2- [1- (4,6-Dimethoxypyrimidin-2-yl) ethyl] aniline

The product from the above step (b) (5.0 g) was added to trifluoroacetic acid (25 ml) and the resulting solution was stirred at room temperature for 3 hours. The solution was evaporated, the residue was triturated with diisopropyl ether and cooled with a dry ice-acetone mixture. The solid is filtered off, washed with diisopropyl ether to give 3.5 g of the desired product, mp. 136-139 ° C.

(g) 1,1,1-Trifluoro-2 '- [1- (4,6-dimethoxypyrimidin-2-yl) ethyl] methanesulfonanilide

The named compound is obtained according to the procedure similar to that described in stage (b) of Example A1, using as the starting product from the above stage (c), so pl. 132-133 ° C.

EXAMPLE A3

1,1,1-Trifluoro-2 '- (4,6-dimethoxy-1,3,5-triazin-2-ylmethyl) methanesulfonanilide

(a) 2,4-Dimethoxy-6- (2-nitrobenzyl) -1,3,5-triazine

To a suspension of 2-nitrophenylacetic acid (3.4 g) in methylene chloride (30 ml), carbonyldiimidazole (3.34 g) is added portionwise and the mixture is stirred at room temperature for 30 minutes. The resulting red solution is added dropwise with stirring to a suspension of the zinc salt of dimethylimidodicarbonimidate (3.0 g) in methylene chloride (25 ml) at -35 ° C. The reaction mixture was stirred at room temperature overnight and poured into water (100 ml). The mixture was extracted with methylene chloride (3 × 50 ml), the combined extracts were dried and evaporated. The resulting red oil is triturated with ether to give 1.41 g of the desired product as a pale brown solid, mp. 91.6-92.3 ° C.

(b) 1,1,1-Trifluoro-2 '- (4,6-dimethoxy-1,3,5-triazin-2-yl-methyl) methanesulfonanilide

The named compound is obtained by methods similar to those described in Example A1 (a), Method 2 (II) and A1 (b), using as the starting product from the above stage (A), so pl. 101-108 ° C.

EXAMPLE A4

N- [3- (4,6-dimethoxypyrimidin-2-ylmethyl) -2-pyridyl] -1,1,1-trifluoromethanesulfonamide

(a) tert.-Butyl- (3-methyl-2-pyridyl) carbamate

A solution of 2-amino-3-methylpyridine (20 g) and di-tert.-butyl dicarbonate (46.8 ml) in dry tetrahydrofuran is boiled for 3 hours and evaporated. The resulting dark brown oil was dissolved in ethyl acetate (400 ml), washed with 1 N. citric acid (3 × 200 ml) and saturated sodium chloride solution, dried and evaporated. The resulting fawn yellow solid residue was crystallized from hexane-diisopropyl ether (1: 2) to give 6.5 g of the desired product as a fawn yellow solid, mp. 135-137 ° C.

(b) tert.-Butyl- [3- (4,6-dimethoxypyrimidin-2-ylmethyl) -2-pyridyl] carbamate

The product from the above step (a) (5 g) was dissolved in dry tetrahydrofuran (100 ml) and tert.-butyllithium (19.2 ml of a 2.5 M solution in heptane) was added dropwise under nitrogen atmosphere at -70 ° C. The mixture was stirred at -70 ° C for 20 minutes, then at 5 ° C for 3 hours. The mixture was cooled to -70 ° C, 4,6-dimethoxy-2-methylsulfonylpyrimidine (5.42 g) was added and stirred at -70 ° C for 1 h and at room temperature overnight. A saturated solution of ammonium chloride (500 ml) was added to the mixture and extracted with ethyl acetate (2 × 100 ml). The combined extracts were washed with saturated sodium chloride solution (50 ml), dried and evaporated. The resulting orange oil is triturated with hexane to give 5.35 g of the desired product as a pale yellow solid, mp. 89-92 ° C.

(c) N- [3- (4,6-dimethoxypyrimidin-2-ylmethyl) -2-pyridyl] -1,1,1-trifluoromethanesulfonamide

The named compound is obtained according to the procedure similar to that described in stage (b) of Example A1, using as the starting product from the above stage (b), so pl. 124-126 ° C.

EXAMPLES A5-A17

By methods analogous to those described above in Example A1, the following compounds of formula Ia can be prepared, wherein A is = CR ⁵ ; Deputy Q represents —CH ₂ -; Deputy R ² represents H; B, D and E take the value = CH-; and each of the substituents R ³ and R ⁴ represents a methoxy group:

Example Y R ⁵ R ¹ Mp (° C) A5 CH N CH ₂ CN 116-117 A6 CH Cl CH ₂ CN 162-163 A7 CH Cl CF ₃ 113-115 A8 CH F CH ₂ CN 162-163 A9 CH F CF ₃ 100-102 A10 CH Me CH ₂ CN A11 CH Me CF ₃ A12 N F CH ₂ CN orange oil A13 N F CF ₃ A14 N Me CH ₂ CN A15 N Me CF ₃ A16 N Cl CH ₂ CN 31 A17 N Cl CF ₃ orange oil

EXAMPLES A18-A20

By methods analogous to those described above in Example A1, the following compounds of formula Ia can be prepared, wherein A represents a nitrogen atom; Deputy Q represents —CH ₂ -; Deputy R ² represents H; B, D and E take the value = CH-; and each of the substituents R ³ and R ⁴ represents a methoxy group:

Example Y R ¹ A18 CH CH ₂ CN A19 N CH ₂ CN A20 N CF ₃

EXAMPLES A21-A68

The following compounds of formula 1a can be prepared by the methods described above, wherein R ² represents a hydrogen atom; each of the substituents R ³ and R ⁴ represents a methoxy group, and the substituent represents —CH—:

Ex Y R ¹ A IN D E A21 CH CF ₃ N N CH CH A22 CH CF ₃ N CH N CH A23 CH CF ₃ N CH CH N A24 CH CF ₃ CH N N CH A25 CH CF ₃ CH N CH N A26 CH CF ₃ CH CH N N A27 CH CF ₃ CCl N N CH A28 CH CF ₃ CCl N CH N A29 CH CF ₃ CCl CH N N A30 CH CF ₃ CF N N CH A31 CH CF ₃ CF N CH N A32 CH CF ₃ CF CH N N A33 CH CH ₂ CN N N CH CH A34 CH CH ₂ CN N CH N CH A35 CH CH ₂ CN N CH CH N A36 CH CH ₂ CN CH N N CH A37 CH CH ₂ CN CH N CH N A38 CH CH ₂ CN CH CH N N A39 CH CH ₂ CN CCl N N CH A40 CH CH ₂ CN CCl N CH N A41 CH CH ₂ CN CCl CH N N A42 CH CH ₂ CN CF N N CH A43 CH CH ₂ CN CF N CH N A44 CH CH ₂ CN CF CH N N A45 N CF ₃ N N CH CH A46 N CF ₃ N CH N CH A47 N CF ₃ N CH CH N A48 N CF ₃ CH N N CH A49 N CF ₃ CH N CH N A50 N CF ₃ CH CH N N

continuation A51 N CF ₃ CCl N N CH A52 N CF ₃ CCl N CH N A53 N CF ₃ CCl CH N N A54 N CF ₃ CF N N CH A55 N CF ₃ CF N CH N A56 N CF ₃ CF CH N N A57 N CH ₂ CN N N CH CH A58 N CH ₂ CN N CH N CH A59 N CH ₂ CN N CH CH N A60 N CH ₂ CN CH N N CH A61 N CH ₂ CN CH N CH N A62 N CH ₂ CN CH CH N N A63 N CH ₂ CN CCl N N CH A64 N CH ₂ CN CCl N CH N A65 N CH ₂ CN CCl CH N N A66 N CH ₂ CH CF N N CH A67 N CH ₂ CN CF N CH N A68 N CH ₂ CN CF CH N N

EXAMPLES A69-A125

The following compounds of formula Ia can be prepared by the methods described above, wherein R ² is H; each of the substituents R ³ and R ⁴ represents a methoxy group; A represents = CR ⁵ ; and the substituent Q represents —CH ₂ -:

Ex Y R ¹ R ⁵ B D E M Pt (° C) A69 CH CF ₃ N N CH CH A70 CH CF ₃ N CH N CH A71 CH CF ₃ N CH CH N A72 CH CF ₃ Cl N CH CH A73 CH CF ₃ Cl CH N CH A74 CH CF ₃ Cl CH CH N A75 CH CF ₃ F N CH CH A76 CH CF ₃ F CH N CH A77 CH CF ₃ F CH CH N A78 CH CH ₂ CN N N CH CH A79 CH CH ₂ CN N CH N CH A80 CH CH ₂ CN N CH CH N

continuation A81 CH CH ₂ CN Cl N CH CH A82 CH CH ₂ CN Cl CH N CH A83 CH CH ₂ CN Cl CH CH N A84 CH CH ₂ CN F N CH CH A85 CH CH ₂ CN F CH N CH A86 CH CH ₂ CN F CH CH N A87 N CF ₃ H N CH CH A88 N CF ₃ H CH N CH A89 N CF ₃ H CH CH N A90 N CF ₃ Cl N CH CH A91 N CF ₃ Cl CH N CH A92 N CF ₃ Cl CH CH N A93 N CF ₃ F N CH CH A94 N CF ₃ F CH N CH A95 N CF ₃ F CH CH N A96 N CH ₂ CN H N CH CH A97 N CH ₂ CN H CH N CH A98 N CH ₂ CN H CH CH N A99 N CH ₂ CN Cl N CH CH A100 N CH ₂ CN Cl CH N CH A101 N CH ₂ CN Cl CH CH N A102 N CH ₂ CN F N CH CH A103 N CH ₂ CN F CH N CH A104 N CH ₂ CN F CH CH N A105 CH CH ₂ CN H CH CCl CH 175-176 A106 CH CH ₂ CN H CH CF CH 110-111 A107 CH CF ₃ H CH CF CH 112-114 A108 CH CF ₃ H CH CBr CH 87-88 A109 CH CH ₂ CN F CH CF CH 185-186 A110 N CH ₂ CN H CH CH CH 186-188 A111 CH CF ₃ F CH CF CH 106-107 A112 CH CH ₂ Cl F CH CF CH 140-141 A113 CH Me F CH CF CH 173-174 A114 CH CH ₂ CN Cl CH CCl CH 211-214 A115 CH CH ₂ CN F CH CMe CH 178-181

continuation A116 CH CH ₂ Cl Cl CH CH CH 142-143 A117 N CH ₂ CN Cl CH CCl CH yellow oil A118 CH CH ₂ CN F CH C (OMe) CH 161-163 A119 CH CH ₂ CN Ome CH CF CH 189-190 A120 CH CH ₂ CN F CH C (OEt) CH 115-116 A121 N CH ₂ Cl F CH CH CH 141-142 A122 CH CH ₂ Cl F CH CH CH 138-139 A123 CH CH ₂ Br F CH CH CH 137-138 A124 CH CH ₂ CF ₃ F CH CH CH 141-142 A125 CH CH ₂ CF ₃ Cl CH CH CH 153-154

EXAMPLES A126-A127

The following compounds of formula Ia can be prepared by the methods described above, wherein R ² is H; each of the substituents R ³ and R ⁴ represents a methoxy group; A represents = CR ⁵ ; and the substituent Q is —CHMe—:

Example Y R ¹ R ⁵ B D E Mp (° C) A126 CH CH ₂ CN H CH CH CH 133-135 A127 CH CH ₂ CN Cl CH CH CH 133-135

EXAMPLE B

EXAMPLE B1

N- [3- (4,6-Dimethoxypyrimidin-2-ylthio) -1,5-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide and N- [5- (4,6- dimethoxypyrimidin-2-ylthio) -1,3-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide

(a) 5- (4,6-dimethoxypyrimidin-2-ylthio) -3-methyl-4-nitro-1H-pyrazole

To a solution of 4,6-dimethoxy-2-mercaptopyrimidine (4.65 g) in an aqueous solution of potassium hydroxide (1.7 g in 75 ml of water) is added dropwise a solution of 1,4-dinitro-3-methylpyrazole (4.65 g) dissolved in minimum amount of ethanol. The reaction proceeds exothermically and upon completion, the mixture is stirred for 45 minutes. The precipitate formed is filtered off, washed with fresh water, dried, and 6.3 g of the desired product are obtained, mp. 175-176 ° C.

(b) 5- (4,6-Dimethoxypyrimidin-2-ylthio) -1,3-dimethyl-4-nitro-1H-pyrazole and 3- (4,6-dimethoxypyrimidin-2-ylthio) -1,5-dimethyl -4-nitro-1H-pyrazole

To a mixture of a 60% suspension of sodium hydride (0.47 g) and dry dimethylformamide (20 ml), the product from the above step (a) (3.15 g) is added portionwise with stirring and cooling in an ice bath. Upon completion of the addition, the mixture was stirred for 10 minutes at room temperature and methyl iodide (1.7 g) was added dropwise. The mixture was stirred at room temperature for 2.5 h, poured ice water (50 ml), extracted with ethyl acetate (3 × 50 ml), the combined extracts washed with water and dried with magnesium sulfate. By filtration and subsequent evaporation, the crude product is isolated as an oil.

The crude product is subjected to flash chromatography on silica gel (eluent ethyl acetate-petroleum ether 40-60 °, 1: 1) and two new products are isolated. By evaporation of fractions containing pure substances, two different solid products are isolated.

According to the results of thin-layer chromatography (TLC) on silica gel plates (eluent ethyl acetate-petroleum ether 40-60 °, 1: 1), one product has an R _{f of} about 0.75 (apparently 5- (4,6-dimethoxypyrimidine-2- ylthio) -1,3-dimethyl-4-nitro-1H-pyrazole) and the other R _{f of} about 0.3 (apparently 3- (4,6-dimethoxypyrimidin-2-ylthio) -1,5- dimethyl-4-nitro-1H-pyrazole). The product yield with R _f 0.75 is 1.3 g, so pl. 124-125 ° C. The product yield with R _f 0.3 is 0.82 g, so pl. 155-156 ° C.

(c) 3- (4,6-Dimethoxypyrimidin-2-ylthio) -1,5-dimethyl-1H-pyrazol-4-amine and 5- (4,6-dimethoxypyrimidin-2-ylthio) -1,3-dimethyl -1H-pyrazole-4-amine

A mixture of the product from step (b) (R _f 0.3) (2.4 g) and tin (II) chloride dihydrate (8.7 g) in ethanol (100 ml) was stirred at the boil for 4 hours. The ethanol was evaporated in in vacuo, the residue was stirred with water (100 ml) and made basic with solid sodium bicarbonate. Ethyl acetate (100 ml) was added, the resulting emulsion was filtered through a kieselguhr pad and the organic layer was separated. The precipitate was washed with ethyl acetate (total 75 ml), and the aqueous layer was extracted with ethyl acetate (2 × 50 ml). The combined organic layers were washed with water (50 ml), separated and dried with magnesium sulfate. After evaporation of ethyl acetate, an oil remains which crystallizes. The crude product is purified by flash chromatography on silica gel (eluent ethyl acetate), a new product is isolated with R _f 0.3 (TLC on silica gel, eluent ethyl acetate). By evaporation of the fractions containing the pure new product, 1.33 g of a solid are obtained with mp. 104-105 ° C.

Another isomer was obtained by a similar method, yield 2.6 g, mp. 74-75 ° C.

(d) N- [3- (4,6-Dimethoxypyridin-2-ylthio) -1,5-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide (B1a) and N- [5 - (4,6-dimethoxypyrimidin-2-ylthio) -1,3-dimethyl-1H-pyrazol-4-yl] 1,1,1-trifluoromethanesulfonamide (B1b)

To a solution of aminopyrazole from the above step (c) (R _f 0.3, 1.2 g) in dry methylene chloride (30 ml) with stirring and at -60 ° C (cooling in a dry ice-acetone bath) is added dropwise a solution of trifluoromethanesulfonic anhydride (1.2 g ) in dry methylene chloride (10 ml). Upon completion of the addition, the temperature of the mixture was slowly brought to room temperature and stirred overnight. The resulting dark red solution was diluted with 100 ml of fresh methylene chloride, washed with water (25 ml), 1 M HCl (25 ml) and water (25 ml). The layers were separated, the organic layer was dried with magnesium sulfate, filtered, evaporated to give a semi-solid dark red substance. Flash chromatography on silica gel (eluent ethyl acetate-petroleum ether 40-60 °, 1: 1) isolated a new product with R _f 0.5 (TLC on silica gel plates, eluent ethyl acetate-petroleum ether 40-60 °, 1: 1). The fractions containing the pure new product are evaporated to give the desired product (B1a) as a white solid. Yield 0.83 g, mp. 203-204 ° C.

Another isomer (B1b) was obtained by a similar method, yield 1.8 g, mp. 145-146 ° C.

EXAMPLE B2

1-Cyano-N- [3- (4,6-dimethoxypyrimidin-2-ylthio) -1,5-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide (B2a) and 1-cyano -N- [5- (4,6-dimethoxypyrimidin-2-ylthio) -1,3-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide (B2b)

The aminopyrazole from step (c) of Example B1 (R _f 0.3, 0.8 g) was dissolved in dry methylene chloride (10 ml) and dry pyridine (0.23 g) was added with stirring. The mixture was cooled to −78 ° C. (dry ice-acetone bath) and cyanomethanesulfonyl chloride (0.4 g, 0.00285 mol) was added portionwise. The mixture was allowed to slowly warm to room temperature and stirred for 2 days. The mixture was then diluted with ethyl acetate to 100 ml and washed with water, 1 M HCl, again with water and the layers were separated. The organic layer was filtered, dried with magnesium sulfate, filtered and evaporated. The residue was subjected to flash chromatography on silica gel (diethyl ether eluent) to give a new product with R _f 0.4 (approximately) (TLC on silica gel, diethyl ether eluent).

The fractions with the pure product are combined, evaporated to obtain the desired product (B2a) as a yellow solid (700 mg), mp. 166-167 ° C.

In a similar manner, another isomer (B2b) is obtained in the form of a solid, yield 1.6 g.

EXAMPLE B3

1-Cyano-N- [4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methyl-1H-pyrazol-5-yl] methanesulfonamide (B3a) and 1-cyano-N- [4- (4, 6-dimethoxypyrimidin-2-ylthio) -1-methyl-1H-pyrazol-3-yl] methanesulfonamide (B3b)

(a) 2- (4,6-Dimethoxypyrimidin-2-ylthio) -3- (dimethylamino) acrylonitrile

A mixture of dimethyl acetal dimethylformamide (5.8 g) and 2- (4,6-dimethoxypyrimidin-2-ylthio) acetonitrile (5.1 g) was stirred at 100 ° C in an oil bath for 5 hours and left overnight at room temperature. The crude solid was triturated with diisopropyl ether to give the desired product as a yellow solid in 5.4 g yield.

(b) 4- (4,6-Dimethoxypyrimidin-2-ylthio) -1-methylpyrazol-3-amine and 4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methylpyrazol-5-amine

To a mixture of the product from the above step (a) (2.6 g) and glacial acetic acid (10 ml) was added dropwise methylhydrazine (1.0 g), heated in an oil bath to 100 ° C and held for 3 hours. The mixture was allowed to cool and poured into water (100 ml). The mixture was then neutralized with solid sodium bicarbonate and extracted with ethyl acetate (3 × 75 ml). The combined organic layers were washed with water (30 ml), separated, dried with magnesium sulfate, filtered and evaporated. The oil obtained is subjected to flash chromatography on silica gel (eluent is pure ethyl acetate), and mainly one product is obtained (R _f 0.3, TLC on silica gel, ethyl acetate eluent). The fractions with the pure product were combined, evaporated to give an off-white product with a yield of 2.2 g. A ¹ H NMR spectrum indicated that it was a 50/50 mixture of two possible isomeric products. The resulting isomers were separated using preparative high pressure liquid chromatography. Evaporation of fractions containing separate pure isomers gives both products as colorless crystals.

One of the obtained products (A) was isolated with a yield of 480 mg, mp. 110-111 ° C (apparently 4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methylpyrazol-5-amine). Another product (B) (apparently 4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methylpyrazol-3-amine) was isolated in a yield of 800 mg, mp 160-161 ° C.

(c) 1-Cyano-N- [4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methyl-1H-pyrazol-5-yl] methanesulfonamide and 1-cyano-N- [4- (4, 6-dimethoxypyrimidin-2-ylthio) -1-methyl-1H-pyrazol-3-yl] methanesulfonamide

A solution of pyrazole (A) from the above step (b) (475 mg) in methylene chloride (10 ml) was cooled to -78 ° C (in a dry ice-acetone bath) and pyridine (0.15 ml) was added with stirring. Using a syringe, a solution of cyanomethanesulfonyl chloride (250 ml) in methylene chloride (1 ml) was added dropwise, then allowed to slowly warm to room temperature and stirred overnight. The mixture was diluted with ethyl acetate to 100 ml, washed with water (30 ml), diluted with hydrochloric acid (2 × 30 ml) and saturated sodium chloride solution (30 ml). The organic layer was separated, dried with magnesium sulfate, filtered, evaporated to give an off-white solid product (apparently 1-cyano-N- [4- (4,6-dimethoxypyrimidin-2-ylthio) -1-methyl-1H- pyrazol-5-yl] methanesulfonamide) (B3a). After recrystallization from ethanol, 350 mg of product is isolated, mp. 206-207 ° C. Another isomer (B3b) is obtained by a similar method, using pyrazole (B) as the starting material from the above stage (b), yield 650 mg, mp 147-148 ° C.

EXAMPLE B4

N- [3- (4,6-Dimethoxy-1,3,5-triazin-2-yl) -1,5-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide

(a) Diethyl- (5-methyl-4-nitropyrazol-3-yl) malonate

To a mixture of a 60% suspension of sodium hydride (2.3 g) in dry tetrahydrofuran (100 ml), diethyl malonate (9.4 g) was added dropwise with stirring and cooling in an ice bath, stirred for 10 minutes and then in small portions for 10 minutes 1,5-dinitro-3-methylpyrazole (5.0 g) was added while maintaining a temperature of 10-12 ° C. The mixture was stirred at room temperature for 30 minutes and glacial acetic acid (3 ml) was added dropwise over about 5 minutes. The mixture was diluted with ethyl acetate (400 ml), washed with water (2 × 30 ml), the organic layer was separated, dried with magnesium sulfate, filtered and evaporated. The residue is an oil that crystallizes upon trituration with 60-80 ° C perrole ether. 7.5 g of the desired product are obtained in the form of a pale yellow solid, mp. 100-102 ° C.

(b) (5-Methyl-4-nitropyrazol-3-yl) acetic acid

A mixture of potassium hydroxide (5.9 g), the product of the previous step (7.5 g) and 50% aqueous ethanol (100 ml) is boiled with stirring for 1.5 hours, allowed to cool, evaporated almost to dryness, diluted with water (100 ml) and acidified with concentrated hydrochloric acid. The resulting mixture was heated to approximately 80 ° C for 0.5 hours, cooled and evaporated to dryness. The residue was taken up in ethyl acetate (100 ml), washed with water (2 × 20 ml), the organic layer was separated, dried with magnesium sulfate, filtered and evaporated. Obtain 3.85 g of the desired product as a yellow solid.

(c) Methyl- (5-methyl-4-nitropyrazol-3-yl) acetate

The product from the previous step (3.85 g) was dissolved in methanol (75 ml) containing a few drops of concentrated sulfuric acid. The resulting mixture was boiled with stirring for 2 hours and allowed to cool. The methanol was evaporated in vacuo, the residue was dissolved in ethyl acetate, washed with water, the organic layer was separated, dried with magnesium sulfate, filtered and evaporated. Obtain 4.0 g of the desired product in the form of a cream-colored solid, so pl. 132-133 ° C.

(d) Methyl (1,5-dimethyl-4-nitro-1H-pyrazol-3-yl) acetate and methyl (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl) acetate

To the mixture of potassium carbonate (2.5 g) and dimethylformamide (30 ml), the product from the previous step (3.3 g) is added with stirring, methyl iodide (2.6 g) is added in one portion, and a moderately exothermic reaction is observed. The mixture was stirred overnight at room temperature, diluted with 100 ml of water and extracted with diethyl ether (4 × 50 ml). The combined extracts were washed with water (30 ml), separated, dried with magnesium sulfate, filtered and evaporated. Obtain 3.2 g of the desired isomeric mixture of products in the form of an oily solid.

(e) (1,5-Dimethyl-4-nitro-1H-pyrazol-3-yl) acetic acid and (1,3-dimethyl-4-nitro-1H-pyrazol-5-yl) acetic acid

To a solution of the product from the previous step (3.2 g) in ethanol (25 ml), a solution of potassium hydroxide (1.7 g) in water (25 ml) is added with stirring and boiled with stirring for 3 hours. The mixture is evaporated almost to dryness, diluted with 50 ml of water , acidified with concentrated hydrochloric acid and evaporated. The residue was dissolved in ethyl acetate, washed with water, dried with magnesium sulfate, filtered and evaporated. Obtain 3.2 g of the desired isomeric mixture of products in the form of a solid orange color.

(e) 2- (1,3-Dimethyl-4-nitro-1H-pyrazol-5-ylmethyl) -4,6-dimethoxy-1,3,5-triazine and 2- (1,5-dimethyl-4- nitro-1H-pyrazol-3-ylmethyl) -4,6-dimethoxy-1,3,5-triazine

The product from the previous step (2.56 g) was dissolved in methylene chloride (50 ml) in a nitrogen atmosphere, which was maintained during all subsequent operations. Carbonyldiimidazole (2.0 g) was added to the mixture and stirred for 30 minutes. The resulting mixture was added dropwise with stirring to a suspension of the zinc salt of dimethylimidodicarbonimidate (2.1 g) in methylene chloride (25 ml) at -35 ° C. The reaction mixture was allowed to warm to room temperature and was stirred overnight. Water (50 ml) and methylene chloride (50 ml) were added to the mixture, filtered through kieselguhr, the layers were separated, the aqueous layer was extracted with methylene chloride (3 × 30 ml). The combined organic layers were washed with water, dried with magnesium sulfate, evaporated to give 3.8 g of crude product. Silica gel flash chromatography (eluent ethyl acetate) gave two new products having an R _{f of} 0.6 and about 0.4. The fractions containing the products are evaporated and get:

R _f 0.6: 1.0 g of 2- (1,3-dimethyl-4-nitro-1H-pyrazol-5-ylmethyl) -4,6-dimethoxy-1,3,5-triazine as a crystalline solid and

R _f 0.4: 1.0 g 2- (1,5-dimethyl-4-nitro-1H-pyrazol-3-ylmethyl) -4,6-dimethoxy-1,3,5-triazine, m.p. 145 ° C.

(g) 2- (4-amino-1,5-dimethyl-4-nitro-1H-pyrazol-3-ylmethyl) -4,6-dimethoxy-1,3,5-triazine

To a suspension of 10% palladium on charcoal (approximately 10 mg) in water (5 ml), a solution of sodium borohydride (0.13 ml) in water (5 ml) is added. Nitrogen was passed through the mixture and a solution of the product from the previous step with R _f 0.4 (0.5 g) in methanol (30 ml) was added dropwise over 5 minutes. The mixture was kept at room temperature for 30 minutes, after which acetic acid (1 ml) was added. The mixture was filtered through kieselguhr, washed with methanol and evaporated almost to dryness. The residue was diluted with 15 ml of water, neutralized with solid sodium bicarbonate, extracted with ethyl acetate (3 × 30 ml), dried with magnesium sulfate, filtered and evaporated. 400 mg of the desired product is obtained in the form of a viscous orange oil.

(h) N- [3- (4,6-Dimethoxy-1,3,5-triazin-2-yl) -1,5-dimethyl-1H-pyrazol-4-yl] -1,1,1-trifluoromethanesulfonamide

To a solution of the product from the previous step (0.4 g) and pyridine (0.13 ml) in methylene chloride (15 ml), a solution of trifluoromethanesulfonic anhydride (0.43 g) in methylene chloride (5 ml) was slowly added dropwise with stirring at -60 ° C. The mixture was allowed to slowly warm to room temperature and stirred for another 24 hours. Then the mixture was washed with water (10 ml), separated, dried with magnesium sulfate, filtered and evaporated. 100 mg of the desired product is obtained in the form of a pale yellow viscous oil.

EXAMPLE B5

1-cyano-N- [5- (4,6-dimethoxypyrimidin-2-ylthio) -1,2-dimethyl-1H-imidazol-4-yl] metal sulfonamide

(a) 1,2-Dimethyl-4-bromo-5-nitro-1H-imidazole and 1,2-dimethyl-5-bromo-4-nitro-1H-imidazole

2-Methyl-4-bromo-5-nitroimidazole (35 g) was dissolved in an aqueous solution of sodium hydroxide (7 g). At room temperature, dimethyl sulfate (21.3 g) was added dropwise and the reaction mixture was stirred for 2 hours. The precipitate was filtered off, washed with water, dried, and 33 g of a mixture of isomers were obtained, which were separated by chromatography (eluent, petroleum ether 60-80 ° - ethyl acetate, 8 : 2). 9.4 g of 1,2-dimethyl-4-bromo-5-nitro-1H-imidazole are isolated, m.p. 98-99 ° C and 19.3 g of 1,2-dimethyl-5-bromo-4-nitro-1H-imidazole, mp 160-162 ° C.

(b) 5- (4,6-Dimethoxypyrimidin-2-ylthio) -1,2-dimethyl-4-nitro-1H-imidazole

To a solution of 4,6-dimethoxy-2-mercaptopyrimidine (3.0 g) in an aqueous solution of sodium hydroxide (0.7 g in 100 ml of water), a solution of 1,2-dimethyl-5-bromo-4-nitro-1H-imidazole is added dropwise ( 3.9 g) in ethanol (50 ml) and the mixture was stirred at room temperature for 6 hours. The precipitate formed was filtered off, washed with water, dried and recrystallized from acetonitrile. Obtain 3.1 g of the desired product, so pl. 228-230 ° C.

(c) 2,2,2-Trifluoro-N- [5- (4,6-dimethoxypyrimidin-2-ylthio) -1,2-dimethyl-1H-imidazol-4-yl] acetamide

A mixture of the product from the previous step (7.0 g), trifluoroacetic acid (130 ml), trifluoroacetic anhydride (18 ml) and iron powder (5.0 g) is heated with stirring to 70 ° C and kept at this temperature for 8 hours. The mixture is filtered, the filtrate is poured onto ice water, alkalinized with 5 N. sodium hydroxide solution and extracted with ethyl acetate. The combined extracts are dried with magnesium sulfate, the solvent is evaporated, the residue is purified by chromatography (eluent, petroleum ether 60-80 ° - ethyl acetate, 8: 2), 5.0 g of the desired product are obtained, mp. 160-162 ° C.

(g) 5- (4,6-dimethoxypyrimidin-2-ylthio) -1,2-dimethyl-1H-imidazol-4-amine

Potassium carbonate (1.5 g) was added to a solution of the product from the previous step (5.4 g) in methanol (200 ml) and the reaction mixture was boiled for 6 hours. The mixture was filtered, the filtrate was evaporated, the residue was recrystallized from acetonitrile, and 2.6 g of the desired product was obtained.

(e) 1-cyano-N- [5- (4,6-dimethoxypyrimidin-2-ylthio) -1,2-dimethyl-1H-imidazol-4-yl] methanesulfonamide

Pyridine (0.3 g) was added to a solution of the product from the previous step (1.0 g) in methylene chloride (10 ml), cooled to -45 ° C, and cyanomethyl sulfonyl chloride (0.5 g) was added in one portion. The mixture was stirred at -45 ° C for 30 minutes, allowed to warm to room temperature and stirred overnight at room temperature. Then the mixture was poured into water, extracted with ethyl acetate and purified by chromatography (eluent petroleum ether 60-80 ° - ethyl acetate, 8: 2) to obtain 0.7 g of the desired product, so pl. 223-225 ° C.

EXAMPLE B6

1-cyano-N- [2- (4,6-dimitoxypyrimidin-2-ylthio) -3-thienyl] methanesulfonamide

(a) 4,6-Dimethoxy-2- (3-nitro-2-thienylthio) pyrimidine

To a solution of sodium hydroxide (1.2 g) in water (50 ml), 4,6-dimethoxy-2-mercaptopopyrimidine (5.3 g) was added and the mixture was stirred at room temperature for 15 minutes. A solution of 2-chloro-3-nitrothiophene (5.0 g) in ethanol (50 ml) was added to the mixture, stirred at room temperature for 6 hours, the precipitate formed was filtered off, washed with water, dried, and 7.6 g of the desired product were obtained, so pl. 199-201 ° C.

(b) N- [2- (4,6-Dimethoxypyrimidin-2-ylthio) -3-thienyl] -2,2,2-trifluoroacetamide

A mixture of the product from the previous step (2.0 g), trifluoroacetic acid (50 ml), trifluoroacetic anhydride (5.0 ml) and iron powder (1.8 g) are heated with stirring to 70 ° C and kept at this temperature for 8 hours. The mixture is filtered, the filtrate is poured into ice water, alkalinized with 5 N. a solution of sodium hydroxide, extracted with ethyl acetate, dried with magnesium sulfate and evaporated to a small volume. The product crystallizes, giving 1.2 g of the desired product, so pl. 88-90 ° C.

(c) 2- (4,6-Dimethoxypyrimidin-2-ylthio) thiophen-3-amine

Potassium carbonate (1.0 g) was added to a solution of the product from the previous step (2.2 g) in methanol (30 ml), the reaction mixture was heated with stirring to 40 ° C and held at this temperature for 6 hours. The mixture was cooled, filtered, and the filtrate was evaporated. , the residue is purified by chromatography (eluent petroleum ether 60-80 ° - ethyl acetate, 8: 2), 1.0 g of the desired product is obtained in the form of an orange oil.

(g) 1-Cyano-N- [2- (4,6-dimethoxypyrimidin-2-ylthio) -3-thienyl] methanesulfonamide

A solution of the product from the previous step (1.2 g) and pyridine (1.0 ml) in methylene chloride (10 ml) was cooled to -78 ° C and a solution of cyanomethyl sulfonyl chloride (0.6 g) in methylene chloride (5 ml) was added dropwise while maintaining the temperature in the range from -78 to -60 ° C. The mixture was stirred at −78 ° C. for 15 minutes, allowed to warm to room temperature and stirred for 16 hours. Then, the mixture was poured into water and extracted with methylene chloride. The combined extracts were dried with magnesium sulfate, the solvent was evaporated. The solid residue is purified by chromatography (eluent petroleum ether 60 - 80 ° - ethyl acetate, 8: 2), 0.4 g of the desired product is obtained, mp. 118-120 ° C.

EXAMPLE B7

N- [2- (4,6-Dimethoxypyrimidin-2-ylthio) -3-thienyl] -1,1,1-trifluoromethanesulfonamide

A solution of the product from step (c) of Example B6 (1.0 g) and pyridine (0.6 ml) in methylene chloride (25 ml) is cooled to -78 ° C and a solution of trifluoromethanesulfonic anhydride (1.1 g) in methylene chloride (5 ml) is added dropwise. keeping the temperature between -78 and -60 ° C. The mixture was stirred at -78 ° C for 15 minutes, allowed to warm to room temperature and stirred overnight at room temperature. Then the mixture is poured into water, extracted with methylene chloride. The combined extracts were dried with magnesium sulfate, the solvent was evaporated. The solid residue is purified by chromatography (eluent petroleum ether 60-80 ° - ethyl acetate, 8: 2) to obtain the desired product (B7a), so pl. 103-104 ° C, as well as the corresponding compound, where the substituent R ² represents —SO ₂ CF ₃ (R7b), mp 136-138 ° C.

EXAMPLE B8

The following compounds of formula 16 can be prepared by the methods described above, wherein R ² represents a hydrogen atom; each of the substituents R ³ and R ⁴ represents a methoxy group, and the substituent Q represents —CH ₂ -:

Y A IN D R ¹ CH S CH CH CF ₃ CH N (Me) CH CH CF ₃ CH S CH N CF ₃ CH S N CH CF ₃ CH N (Me) CH N CF ₃ CH N (Me) N CH CF ₃ CH CH S CH CF ₃ CH CH N (Me) CH CF ₃ CH CH N (Me) CH CF ₃ CH CH S N CF ₃ CH N S CH CF ₃ CH N N (Me) CH CF ₃ CH CCl S CH CF ₃ CH CCl N (Me) N CF ₃ CH CCl S N CF ₃ CH CCl N (Me) N CF ₃ CH CF S CH CF ₃

continuation CH CF N (Me) N CF ₃ CH CF S N CF ₃ CH CF N (Me) N CF ₃ CH CH CH S CF ₃ CH CH CH N (Me) CF ₃ CH N CH S CF ₃ CH CH N S CF ₃ CH CH N N (Me) CF ₃ CH N CH N (Me) CF ₃ CH CCl CH S CF ₃ CH CCl CH N (Me) CF ₃ CH CCl N S CF ₃ CH CCl N N (Me) CF ₃ CH CF CH S CF ₃ CH CF CH N (Me) CF ₃ CH CF N S CF ₃ CH CF N N (Me) CF ₃ N S CH CH CF ₃ N N (Me) CH CH CF ₃ N S CH N CF ₃ N S N CH CF ₃ N N (Me) CH N CF ₃ N N (Me) N CH CF ₃ N CH S CH CF ₃ N CH N (Me) CH CF ₃ N CH N (Me) CH CF ₃ N CH S N CF ₃ N N S CH CF ₃ N N N (Me) CH CF ₃ N CCl S CH CF ₃ N CCl N (Me) N CF ₃ N CCl S N CF ₃ N CCl N (Me) N CF ₃ N CF S CH CF ₃ N CF N (Me) N CF ₃

continuation N CF S N CF ₃ N CF N (Me) N CF ₃ N CH CH S CF ₃ N CH CH N (Me) CF ₃ N N CH S CF ₃ N CH N S CF ₃ N CH N N (Me) CF ₃ N N CH N (Me) CF ₃ N CCl CH S CF ₃ N CCl CH N (Me) CF ₃ N CCl N S CF ₃ N CCl N N (Me) CF ₃ N CF CH S CF ₃ N CF CH N (Me) CF ₃ N CF N S CF ₃ N CF N N (Me) CF ₃ CH S CH CH CH ₂ CN CH N (Me) CH CH CH ₂ CN CH S CH N CH ₂ CN CH S N CH CH ₂ CN CH N (Me) CH N CH ₂ CN CH N (Me) N CH CH ₂ CN CH CH S CH CH ₂ CN CH CH N (Me) CH CH ₂ CN CH CH N (Me) CH CH ₂ CN CH CH S N CH ₂ CN CH N S CH CH ₂ CN CH N N (Me) CH CH ₂ CN CH CCl S CH CH ₂ CN CH CCl N (Me) N CH ₂ CN CH CCl S N CH ₂ CN CH CCl N (Me) N CH ₂ CN CH CF S CH CH ₂ CN CH CF N (Me) N CH ₂ CN CH CF S N CH ₂ CN

continuation CH CF N (Me) N CH ₂ CN CH CH CH N (Me) CH ₂ CN CH N CH S CH ₂ CN CH CH N S CH ₂ CN CH CH N N (Me) CH ₂ CN CH N CH N (Me) CH ₂ CN CH CCl CH S CH ₂ CN CH CCl CH N (Me) CH ₂ CN CH CCl N S CH ₂ CN CH CCl N N (Me) CH ₂ CN CH CF CH S CH ₂ CN CH CF CH N (Me) CH ₂ CN CH CF N S CH ₂ CN CH CF N N (Me) CH ₂ CN N S CH CH CH ₂ CN N N (Me) CH CH CH ₂ CN N S CH N CH ₂ CN N S N CH CH ₂ CN N N (Me) CH N CH ₂ CN N N (Me) N CH CH ₂ CN N CH S CH CH ₂ CN N CH N (Me) CH CH ₂ CN N CH N (Me) CH CH ₂ CN N CH S N CH ₂ CN N N S CH CH ₂ CN N N N (Me) CH CH ₂ CN N CCl S CH CH ₂ CN N CCl N (Me) N CH ₂ CN N CCl S N CH ₂ CN N CCl N (Me) N CH ₂ CN N CF S CH CH ₂ CN N CF N (Me) N CH ₂ CN N CF S N CH ₂ CN N CF N (Me) N CH ₂ CN N CH CH S CH ₂ CN

continuation N CH CH N (Me) CH ₂ CN N N CH S CH ₂ CN N CH N S CH ₂ CN N CH N N (Me) CH ₂ CN N N CH N (Me) CH ₂ CN N CCl CH S CH ₂ CN N CCl CH N (Me) CH ₂ CN N CCl N S CH ₂ CN N CCl N N (Me) CH ₂ CN N CF CH S CH ₂ CN N CF CH N (Me) CH ₂ CN N CF N S CH ₂ CN N CF N N (Me) CH ₂ CN

EXAMPLE of herbicidal activity A (pre-emergence)

The seeds of the test species, which are listed below, are sown in 8.5 cm ² cups filled with sterile loam to a level of 2 cm from the top and covered with a 2-5 mm loam layer. The cups are watered and then treated by applying the following compounds of Examples to the soil surface, which are prepared as a solution / suspension in a mixture of acetone and a solution of polyoxyethylated (20 moles) monolaurate (wetting agent, 10 g / l) in a volume ratio of 3: 1. The concentration of each test compound and the amount of application are calculated so as to obtain the desired compound consumption rate of 200 l / ha.

After 3-4 weeks of growing in a greenhouse (minimum temperature 16 ° C for species adapted to a temperate climate, 21 ° C for species not suitable for a temperate climate, with a photoperiod of 16 hours), the plants are evaluated visually to identify any herbicidal effect. All differences compared with the untreated control are evaluated on a point scale, in accordance with which:

0 = no effect

1 = 1-24% of the effect,

2 = 25-69% of the effect,

3 = 70-89% of the effect and

4 = 90-100% of the effect.

The following letter symbols are used to indicate plant species in the table below:

a - Triticum aestivum (wheat)

b - Hordeum vulgare (barley)

c - Beta vulgaris (sugar beet)

d - Brassica napus (rapeseed)

d - Alopecurus myosuroides (mouse-tail foxtail)

e - Avena fatua (oatmeal)

f - Elymus repens (wheatgrass)

h - Bromus sterilis (barren bonfire)

and - Viola arvensis (field violet)

K - Stellaria media (asterisk)

l - Galium aparine (bedding)

m - Matricaria inodora (odorless chamomile)

n - Polygonum lapathifolium (highlander pale)

o - Veronica persicae (Veronica persian)

The results are presented below:

Example kg / ha a b in g d e well s and to l m n about A1 0.25 1 1 3 4 2 1 3 1 2 4 3 4 3 4 A3 0.5 0 0 2 4 0 0 0 0 2 2 3 4 2 3 A6 0.25 1 0 3 4 1 0 0 2 4 4 4 4 3 4 A7 0.25 1 0 3 2 1 1 0 0 3 4 3 4 2 4 A8 0.125 2 2 3 4 2 1 2 2 3 4 3 4 2 4 A9 0.125 0 1 2 2 2 0 0 2 3 4 3 4 2 4 A16 0.125 2 1 4 4 2 2 2 1 3 4 4 4 3 4 A17 0.063 0 0 1 3 0 0 0 0 2 3 2 3 2 2 A108 0.5 0 0 2 2 0 0 0 0 2 2 2 4 0 2 A109 0.5 0 0 3 3 0 0 1 0 4 3 3 4 2 4 A111 0.125 0 1 1 1 0 0 0 0 1 1 2 3 0 3 A112 0.125 0 1 2 1 0 0 0 1 3 4 3 4 1 3 A114 0.5 0 0 2 2 0 0 0 0 2 3 1 3 1 3 A115 0.5 0 0 2 2 0 0 0 2 3 4 3 4 3 4 A116 0.25 1 1 2 4 1 0 0 1 3 4 4 4 2 4 B1 0.5 0 1 2 3 1 0 2 1 2 2 3 4 2 3

EXAMPLE of herbicidal activity A (post-emergence)

The plants listed below are grown in a greenhouse (minimum temperature 16 ° C for species adapted to a temperate climate, 21 ° C for species unsuitable for a temperate climate, with a photoperiod of 16 hours) in 8.5 cm ² cups containing sterile loam, and then treated in a spraying chamber at the stage of 3-4 leaves with the compounds of the following Examples, formed as a solution / suspension in a mixture of acetone and a solution of polyoxyethylated, (20 mol) monolaurate (wetting agent, 10 g / l) in a volume ratio and 3: 1. The concentration of each test compound and the amount of application are calculated so as to obtain the desired compound consumption rate of 200 l / ha.

After 3-4 weeks of growing in a greenhouse, plants are evaluated visually to identify any herbicidal effect. All differences compared with the untreated control are evaluated on a point scale, in accordance with which:

0 = no effect

1 = 1-24% of the effect,

2 = 25-69% of the effect,

3 = 70-89% of the effect and

4 = 90-100% of the effect.

To indicate plant species in the table below, the same notation is used as in the Example of herbicidal activity A.

The results are presented below:

Example kg / ha a b in g d e well s and to l m n about Ex Kg / ha a b from d e f g h i j k l m n A1 0.5 0 0 2 4 0 0 0 0 0 2 4 4 2 2 A3 0.5 0 0 1 4 1 0 0 0 1 2 4 4 1 2 A5 0.5 1 1 1 3 1 0 1 1 2 1 2 2 1 2 A6 0.25 1 0 4 4 2 2 2 2 3 3 4 4 3 2 A7 0.25 1 1 2 4 2 2 2 2 3 3 3 4 2 3 A8 0.25 1 0 4 4 2 0 2 0 4 4 4 4 2 2 A9 0.125 1 1 3 4 0 0 1 0 3 3 4 4 2 2 A16 0.032 1 1 3 4 1 0 0 0 2 4 4 3 3 1 A17 0.25 0 0 4 4 0 0 0 0 2 4 4 4 3 1 A109 0.5 1 0 4 4 1 0 1 0 2 3 4 4 2 3 A111 0.25 0 0 2 3 1 0 0 0 0 0 3 3 0 2 A112 0.25 0 0 2 3 0 0 0 0 0 2 4 0 2 A114 0.25 0 0 0 2 0 0 0 0 0 0 2 0 0 0 A115 0.25 0 0 1 4 0 0 0 0 0 2 3 2 3 0 A116 0.25 0 0 4 4 1 0 0 0 2 4 4 2 2 2 A117 0.125 0 0 3 4 0 0 0 0 0 3 4 2 2 2 A118 0.125 0 0 1 0 0 0 0 0 0 0 3 0 3 0 A119 0.063 1 0 1 1 0 0 0 0 0 0 2 0 1 1 IN 1 0.5 0 1 2 4 2 0 1 0 0 3 3 4 1 2

ADDITIONAL EXPERIMENTAL DATA

It was found that in addition to the compounds described in this application, the compounds shown in tables 1 and 4 below are also applicable as herbicides. They are included in the scope of the claims and, thus, further confirm the claimed scope of the invention.

Test 1

Compounds 1-A, 1-B, 1-C and 1-D, shown in table 1 below, are tested for herbicide action against weeds in pre-emergence and post-emergence applications in accordance with the HERBICIDAL EXAMPLES A and B of the description. The test results are shown in tables 2 and 3 below. The results prove that the compounds have a valuable herbicidal effect in pre-emergence and / or post-emergence applications.

Table 1 The compounds of formula (1)

Compound R ¹ Q R ² R ^* Y Link 1-A CH ₂ CF ₃ CH-SCH ₃ N F N Refers to paragraph 1 of the invention 1-B CH ₃ CH-OH N F CH Refers to paragraph 1 of the invention 1-C CH ₂ CI CH-OCH ₃ N F CH Refers to paragraph 1 of the invention 1-D CF ₃ CH-F N F CH Refers to paragraph 1 of the invention table 2 Pre-emergence herbicidal action Compound Dose (GAI / ha) Herbicidal action against Al The EU SE PH SI CH GA MA ST 1-A 75 4 4 4 4 4 4 4 4 4 1-B 75 2 2 2 4 4 4 4 4 4 1-C 75 3 3 4 4 - - 3 4 3 1-D 75 2 3 3 4 - - 4 4 4 Table 3 Post-emergence herbicidal action Compound Dose (GAI / ha) Herbicidal action against Al The EU SE PH SI CH GA MA ST 1-A 75 2 2 2 2 3 3 3 2 2 1-B 75 2 2 2 2 4 4 4 4 4 1-C 75 2 3 2 3 2 3 3 3 2

Abbreviations used in tables 2 and 3:

AI = active ingredient

EU = Echinochloa grus-galli

SE = Setaria lutescens

PH = Pharbitis purpurea

SI = Sinapis alba

CP = Chrysanthemum segetum

GA = Gallium aparine

MA = Matricaria inodora

ST = Stellaria media - = not tested

All differences from the untreated control are evaluated in accordance with the indicator, where 0 is the absence of effect, 1 = 1-24%, 2 = 25-69%, 3 = 70-89% and 4 = 90-100% effect.

Table 4 Herbicides of Formula (I ')

No. R ¹ (R) n R ³ R ⁴ Y X T. pl. (° C) 1 CH2CI 2-ci Och3 Och8 N S-C6H5 58-62 2 CH2Cl 4-NO2 OCH3 OCH3 N S-C6H5 80-82 3 CH2Cl 2-C6H5 OCH9 OCH3 N S-C6H5 resin 4 CH3CF3 2-f OCH3 OCH3 N S-C6H5 56-60 5 CH2CF3 2,4-F2 OCH3 OCH3 N S-C6H5 81-84 6 CH2CF3 4-NO2 OCH3 OCH3 N S-C6H5 resin 7 CH2Cl 2,4-F2 OCH3 OCH3 N S-C2H5 122-123 8 CF3 2,4-F2 OCH3 OCH3 N S-C6H5 72-82 nine CH3 2-f OCH3 OCH3 N S-ch3 resin 10 CH9 2,4-F2 OCH3 OCH3 N S-ch3 resin eleven CH3 2-СОС6Н5 OCH3 OCH3 N S-ch3 resin 12 CH2Cl 2-f OCH3 OCH3 CH S-ch3 resin thirteen CH2Cl N OCH3 OCH3 N S-ch3 resin 14 CH2Cl 2-f OCH3 OCH3 N S-ch3 resin fifteen CH2Cl 2,4-F2 OCH3 OCH3 N S-ch3 resin 16 CH2Cl 4-NO2 OCH3 OCH3 N S-ch3 137-140 17 CH2Cl 4-OCF3 OCH3 OCH3 N S-ch3 resin eighteen CH2Cl 2-C6H5 OCH3 OCH3 N S-ch3 158-161 19 CH2Cl 2-OS6N5 OCH3 OCH3 N S-ch3 124-128 twenty CH2Cl 2-СО2СН3 OCH3 OCH3 N S-ch3 resin 21 CH2Cl 3-CF3 OCH3 OCH3 N S-ch3 resin 22 CH2CF3 2-f OCH3 OCH3 CH S-ch3 resin 23 CH2CF8 2-cl OCH3 OCH3 N S-ch3 115-117 24 CH2CF3 2,4-F2 OCH3 OCH3 N S-ch3 resin 25 CH2CN 2-f OCH3 OCH3 CH S-ch3 147 26 CF3 2-f OCH3 OCH3 N S-ch3 143 29th CF3 4-OCF3 OCH3 OCH3 N S-ch3 72-75 thirty CH2C6H5 2-f OCH3 OCH3 CH S-ch3 resin 31 CH2C6H5 2-f OCH3 OCH3 N S-ch3 72-77 32 NHCO2CH3 2-f OCH3 OCH3 CH S-ch3 113-115 33 CH2Cl 2-f OCH3 OCH3 CH HE 153-155 34 CH2CF3 2-f OCH3 OCH3 CH HE 143-145 35 CH2CN 2-cl OCH3 OCH3 CH HE 172 (dec) 36 CF3 2-f OCH3 OCH3 CH HE 94-96 37 CF3 2-cl OCH3 OCH3 CH HE 120 38 C6H5 2-f OCH3 OCH3 CH HE 153-154

All compounds shown in table 4 above, receive in accordance with the methods described in this invention. These compounds are also tested for herbicidal action in pre-emergence and post-emergence applications.

The tested compounds show herbicidal activity with a rating of “good” to “excellent” (from 70 to 100% compared with the control) in relation to important species of weeds, such as:

Sinapis alba,

Matricaria inodora,

Chrysanthemum segetum,

Avena sativa,

Stellaria media,

Echinochloa crus-galli,

Lolium multiflorum,

Setaria spp,

Abutilon theophrasti,

Amaranthus retroflexus and

Panicum miliaceum

with pre-emergence application at a dose of 0.5 kg or less of the active ingredient per hectare.

In addition, the tested compounds have herbicidal activity with a rating of “good” to “excellent” for important species of weeds, such as:

Sinapis alba,

Echinochloa crus-galli,

Lolium rnultrflorum,

Matricaria inodora,

Chrysanthemum segetum,

Setaria spp.,

Abutilon theophrasti,

Amaranthus retroflexus,

Panicum miliaceum and

Avena sativa

with post-emergence use at a dose of 0.5 kg or less of active ingredient per hectare.

From the above additional data it can be seen that the claimed scope of claims for the compounds of formula (I) is sufficiently substantiated and fully confirmed, and that the aryl groups can be substituted by various substituents without loss of beneficial herbicidal effect. In addition, the substituents X on the CXX bridge 'may be modified within the scope of paragraph 1 to include X or X', which are phenylthio, alkylthio, alkoxy, halogen, hydroxy, and the like. derivatives thereof (or precursors) such as phenoxy.

ADDITIONAL EXPERIMENTAL DATA

The herbicides of the formula (I ') were investigated

Where

No. R ¹ (R) _n R ³ R ⁴ Y X T deputy. (° C) I'-a CHF ₂ - OCH ₃ OCH ₃ CH HE 103-105 I'-b CHF ₂ 2-CH ₂ -OCH ₃ OCH ₃ OCH ₃ CH HE 76-77 I'-s CHF ₂ 2-CH ₂ -CH ₃ OCH ₃ OCH ₃ CH HE 120-121

The compounds shown in the table, obtained by the method presented in the application.

Compounds were tested in the field for herbicidal activity against weeds typical of rice fields.

Verification conditions and results.

Weed seeds were sown in the ground under a 3 cm thick layer of water. The test compounds were used in the form of standard water-based compositions. After processing the plants, they were kept for 28 days in greenhouse conditions. After that, weeds were evaluated by comparison with control (untreated plants). The results are presented below.

Dose
Compound (grams AI / ha) Herbicidal action (effectiveness indicator) against The EU MO SC I'-a 250 5 5 5 65 4 5 5 fifteen 3 5 5 I'-b 250 5 5 5 65 5 5 5 fifteen 5 5 5 I'-s 250 5 5 5 65 5 5 5 fifteen 5 5 5

Designations

EC = Echinochloa oryzicola

MO = Monoochoria vaginalis

SC = Scirpus juncoides

The effectiveness of the compounds is expressed using a rating scale:

0 = no effect - 9% effect;

1 = 10-29%;

2 = 30-49%

3 = 50-69%

4 = 70-89%;

5 = 90-100% effect.

Under the effect is understood the magnitude of the difference in the number of weeds during processing and in control in relation to control.

Claims (9)

1. Sulfonamides of the formula

and their salts, where A is a substituted or unsubstituted benzene ring or a 5-membered or 6-membered substituted or unsubstituted heteroaromatic ring selected from the group consisting of thienyl, pyrazolyl, imidazolyl, pyridyl, where optional substituents are selected from the group consisting of halogen, unsubstituted or substituted alkyl containing 1-4 carbon atoms, unsubstituted or substituted alkoxy, containing 1-4 carbon atoms, nitro, phenyl, phenoxy, benzoyl and alkylcarboxylate containing 1-4 carbon atoms in the alkyl moiety When any alkyl moiety in the last mentioned substituents substituted with one or more halogen atoms, alkoxy groups having 1-4 carbon atoms, cyano and phenyl; Q represents —O—, —S— or a group of the formula —CXX ′; X and X ', which may be the same or different, are each hydrogen, halogen, cyano, alkyl containing 1-8 carbon atoms, or the group -OR ^a , -SR ^a or one of X and X' is hydroxy, and the other takes on the meanings defined above; R ^a represents alkyl containing 1-8 carbon atoms, or phenyl; R ^b represents alkyl containing 1-8 carbon atoms, or phenyl; Y represents nitrogen or a group CR ⁹ ; R ¹ represents alkyl containing 1-8 carbon atoms, unsubstituted or substituted by halogen, cyano, phenyl or alkoxycarbonylamino containing 1-4 carbon atoms in the alkyl moiety, or represents phenyl; R ² represents hydrogen or alkyl containing 1-4 carbon atoms; R ³ and R ⁴ , which may be the same or different, are each alkyl containing 1-4 carbon atoms, an alkoxy group containing 1-4 carbon atoms, or halogen; R ⁹ represents hydrogen, with the proviso that when Q is O or —S—, ring A is a 5-membered substituted or unsubstituted heteroaromatic ring as defined above. 2. The sulfonamides according to claim 1, where R ¹ represents methyl, chloromethyl, bromomethyl, cyanomethyl or trifluoromethyl. 3. The sulfonamides according to claim 1 or 2, where R ² represents hydrogen. 4. Sulfonamides according to any one of claims 1 to 3, where R ³ represents methyl, methoxy group or chlorine, and R ⁴ represents methyl or methoxy group. 5. The sulfonamides according to any one of claims 1 to 4, wherein A is phenyl optionally substituted with F, Cl, Br, methyl or methoxy group, or is pyrazolyl substituted with one or more methyl groups. 6. Sulfonamides according to any one of claims 1 to 5, where Q represents CH ₂ . 7. A herbicidal composition containing 0.01-99 wt.% Of one or more compounds of formula (I) according to any one of claims 1 to 6 and 1-99.99 wt.% Of a suitable carrier and / or surfactant. 8. A method of controlling weeds in areas contaminated with weeds or in which they are expected to occur, comprising applying to the indicated area an effective amount of one or more compounds according to any one of claims 1 to 6. 9. The method of producing a sulfonamide of formula I according to claim 1, where ring A is phenyl, which may have 1-2 substituents selected from a halogen atom, lower alkyl, lower alkoxyl, or is an unsaturated five-membered heterocycle with a sulfur atom or two atoms nitrogen and which may be substituted by two lower alkyls, R ¹ represents a lower alkyl group substituted by halogen atoms, cyano, R ² represents hydrogen, Q represents —S—, a group (CH ₂ ) n which may be substituted by lower alkyl , n = 1 or 2, R ³ and R ⁴ - the same and represent a lower alkoxy group, Y represents nitrogen or a group CR ⁹ , where R ⁹ represents hydrogen, including the interaction of the compounds of formula II

where the values of A, R ¹ , R ² , Q, n, R ³ , R ⁴ , Y are given above, with a sulfonic anhydride of the formula (R ¹ SO ₂ ) ₂ O or a sulfonyl halide of the formula R ¹ SO ₂ Hal, where Hal is halogen.