The acylated aminophenylacetylene or their salts, intermediate phenylsulfonyl, herbicide tool and method of combating weeds

 

(57) Abstract:

The invention relates to novel acylated to aminophenylacetylene General formula I which possess herbicide action and selectivity of action in comparison with the previously known compounds of this series. The compounds may be used in agriculture to control weeds. The acylated aminophenylacetylene correspond to the General formula I, where Z is CH or N, X, Y is halogen, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, mono - or dialkylamino from 1 to 14 carbon atoms in each alkyl part, R1and R2is hydrogen or alkyl with 1 or 2 carbon atoms or together with the nitrogen atom to which they are linked, form a heterocyclic ring with 3 to 8 ring atoms, R3group-R5where R5means hydrogen, alkoxy with 1 to 4 carbon atoms, alkyl with 1 to 6 carbon atoms which may be substituted in the alkyl part 1 to 3 halogen atoms, cycloalkyl with 3 to 8 carbon atoms, mono - or dialkylamino with 1 to 4 carbon atoms in each alkyl part, the group-NH-R6where R6means pyrimidine ring, unsubstituted or substituted two CNS groups with 1 - 4 and the AMI carbon R4is hydrogen, alkyl with 1 to 4 carbon atoms. The invention also relates to intermediate derived phenylsulfonyl formula XVI where R1and R2are specified in the PP.1 - 4 values, if R8means a group NH-tert.-butyl, R9means nitro, amino or a group NR10in which R10mean group R11where R11denotes hydrogen, alkyl with 1 to 6 carbon atoms, or R8means amino, and R9group-NR10where R10has a specified value representing intermediate products to obtain the acylated aminophenylacetylene General formula I on PP.1 to 4. The invention relates to the herbicide agent containing compounds of General formula I or its salt in an effective amount and the target additives, as well as to a method of combating weeds by treatment of the latter or its habitat or plants, seeds or seed plots compounds of formula I or its salt in an effective amount. 4 C. and 3 h.p. f-crystals, 8 PL.

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The invention relates to new derivatives of aminophenylacetic possessing biological activity, more specifically, to the acylated aminophenylacetylene, intermediate penyanyi aminophenylacetylene, have a weed-killing activity (see U.S. patent N 4892946, CL 07 D 239/28, published. 9 January 1990).

Object of the invention is the expansion of the range atsilirovannym of aminophenylacetylene, which can be an active ingredient herbicide tools.

The problem is solved, we offer acylated by aminophenylacetylene General formula (I)

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where R1and R2is hydrogen or alkyl with 1 or 2 carbon atoms or together with the nitrogen atom to which they are linked, form a heterocyclic ring of from 3-8 ring atoms,

R3group - COR5where R5means hydrogen, alkoxy with 1-4 carbon atoms, alkyl with 1-6 carbon atoms which may be substituted in the alkyl part 1 to 3 halogen atoms, cycloalkyl with 3-8 carbon atoms, mono - or dialkylamino with 1-4 carbon atoms in each alkyl part, the group-NH-R6where R6means pyrimidine ring, unsubstituted or substituted two CNS groups with 1-4 carbon atoms, or-SO2R7where R7has the meaning of the radical R5except alkoxy with 1-4 carbon atoms,

R4is hydrogen, alkyl with 1-4 carbon atoms,

X, Y is a halogen, the Oh alkyl part,

Z is CH or N, or their salts.

The compounds of formula (I) may exist as stereoisomers, such as enantiomers, diastereomers, Z - and E-isomers, or salts. Stereoisomers can be obtained by customary methods from mixtures of the stereoisomers or by stereotypically reaction using stereochemical pure starting materials.

Salts of compounds of formula (I) receive due to the fact that hydrogen group-SO2NH - or other azadnia hydrogen atoms (for example, in the group COOH) substitute suitable for agriculture cation. Such salts are, for example, metal salts, in particular salts of alkaline or alkaline earth metals, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines. In addition, the salt formation can be accomplished by attaching acid to basic groups, as, for example, amino -, alkylamino group. Suitable acids are inorganic or organic acids such as, for example, hydrochloric acid, Hydrobromic acid, sulfuric acid, nitric acid.

The first group preferred acylated aminophenylacetylene General formula (II) include coee ring with 4 to 8 ring atoms, or their salts.

The second group preferred acylated aminophenylacetylene General formula (I) include compounds in which X and Y denote halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1-4 carbon atoms, or their salts.

The third group preferred acylated aminophenylacetylene General formula (I) include compounds in which R1and R2together with the nitrogen atom to which they are linked, form a heterocyclic ring with 5 or 6 ring atoms, R3group-COR5where R5denotes hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms which may be substituted in the alkyl part 1 to 3 halogen atoms, cycloalkyl with 3-6 carbon atoms, mono - or dialkylamino with 1-4 carbon atoms in each alkyl part, or group-SO2R7where R7means alkyl with 1-3 carbon atoms which may be substituted by 1 to 3 halogen atoms,

R4is hydrogen, methyl,

X, Y is halogen, alkyl with 1 to 2 carbon atoms, alkoxy with 1 to 2 carbon atoms,

or their salts.

Compounds of General formula (I) or their salts can be obtained by known methods, for example, due to the fact that

a) compound of formula (II)



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where X, Y and Z have the above significance, and R*means unsubstituted or substituted phenyl or alkyl with 1-4 carbon atoms, or

b) sulfonylation formula (IV)

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where R1- R3have the above meaning, is subjected to the interaction with the heterocyclic amine of formula (V)

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where R4X, Y and Z have the above meaning,

or

C) sulfochloride formula (VI)

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where R1- R3have the above meaning, is subjected to the interaction with the heterocyclic amine of the above formula (V) in the presence of cyanate, for example, alkali metal cyanate, such as sodium cyanate or potassium, or

g) a sulfonamide of the above formula (II) is subjected to interaction with the (thio)isocyanate of formula (VII)

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where X, Y and Z have the abovementioned meaning, in the presence of a suitable base, e.g. potassium carbonate or triethylamine.

Sulfonamides of formula (II), sulfonylation formula (IV) and sulphonylchloride formula (VI) are new compounds.

The reaction of compounds of formulas (II) and (III) is preferably carried out in the presence of an employee as catalyst bases in inert solvents, dapnia used solvent. The grounds are used, for example, organic aminoaniline as, for example, 1,8-diazabicyclo[5.4.0]-undec-7-ene, in particular when R*= (substituted) phenyl or trimethylsilyl or triethylaluminium, in particular, when R*= alkyl.

The compounds of formula (II) are obtained, for example, from N-(t-butyl)-sulfonamides of formula (VIII), (IX) and (X) (see formula VIII, Z*= R3NH-).

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Z* = OTHER3Z* = NH2Z* = NO2.

Proceeding from compounds of formula (VIII) in which R1R2, R3have the above for formula (I) values, obtain the compounds of formula (II) by reacting with a strong acid. As strong acids are suitable, for example, mineral acids such as, for example, sulfuric acid or hydrochloric acid, or strong organic acids such as, for example, triperoxonane acid. Removing the t-butyl carried out at a temperature from -20oC to temperature phlegmy the reaction mixture, preferably at a temperature of 0-40oC. Interaction can be performed in the environment of the solvent, for example dichloromethane or trichloromethane.

The compounds of formula (VIII) can be obtained for example from an aniline derivative of the formula (IX) (see formula (VIII), R*= NH

These anilines of the formula (IX) are obtained by known literature methods, for example, from compounds of the formula (X) (see formula (VIII), Z*= NO2) by the reduction of nitro groups, for example, by catalytic hydrogenation or reduction with iron in acetic acid environment.

The compounds of formula (X) can be obtained from benzoate formula (XI) by amidation:

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The formation of amides is carried out by reaction of benzoate formula (XI) in which R0means alkyl, with amines of the formula (XII). Compounds of formulas (XI) and (XII) are known, or they are educti, which can be purchased on the market or these compounds can be obtained analogously to known methods.

Amides of formula (VIII), (IX) and (X) are new compounds.

An alternative method of preparing compounds of the formula (XI). Represents the following synthesis.

On the basis of 2-amino-nitrobenzoic acids of the formula (XIII), for example, 2-amino-4-nitrobenzoic acid of formula (XIIIa), get the corresponding esters of benzoic acid of formula (XIV) in which R0means alkyl, by the usual tarifica the ASS="ptx2">

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By diazotization of the amino group and subsequent interaction with the sulfur dioxide in the presence of copper chloride receive sulfochloride formula (XV).

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By ammonolysis of the compounds of formula (XV) using t-butylamine get sulfonamides of the formula (XI).

Required for the reaction of compounds of formula (II) according to variant a) carbamates of the formula (III) are known from the literature or can be obtained analogously to known methods.

Phenylsulfonylacetate formula (IV) can be obtained by known methods, for example, by reacting compounds of the formula (III), for example, with phosgene.

The interaction of compounds of the formula (IV) with aminoheterocycles formula (V) is preferably carried out in inert aprotic solvents such as, for example, dioxane, acetonitrile or tetrahydrofuran, at temperatures from 0oC to the boiling point of the solvent.

The interaction of sulfochlorides formula (VI) with aminoheterocycles formula (V) and cyanate, for example, sodium cyanate or potassium, carried out, for example, in inert aprotic solvents, such as acetonitrile, if necessary in the presence of osowaniu, for example, 0.5 - 2 equivale predpochtitelno -10oC to 60oC, in particular, from the 15oC to 40oC. as a base or basic aprotic solvent is suitable, for example, pyridine, picoline or lutidine, or their mixture.

(Thio)isocyanates of the formula (VII) can be obtained by known literature methods. The interaction of the (thio)isocyanates of the formula (VII) with compounds of the formula (II) is carried out at a temperature from -10oC to 100oC, preferably from 20oC to 100oC, in an inert aprotic solvent, such as acetone or acetonitrile, in the presence of a suitable base, such as triethylamine or potassium carbonate.

Salts of compounds of formula (I) preferably get in an inert solvent, for example, water, methanol, acetone, dichloromethane, tetrahydrofuran, toluene or heptane, at a temperature of from 0oC to 100oC. Suitable bases for obtaining the proposed salts are, for example, carbonates of alkali metals such as potassium carbonate, hydroxide of alkali and alkaline earth metals such as sodium hydroxide, potassium or calcium, ammonia, or suitable aminoaniline as, for example, triethylamine or ethanolamine. As acids for salt formation are suitable, H2">

The term "inert solvent" refers to solvents which are inert under the respective reaction conditions, but which should not be inert under any conditions.

Given the above information that some of the intermediate compounds are new, more object are derived phenylsulfonyl General formula (XVI)

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where R1and R2have the above value, a R8and R9have the following meanings:

if R8means a group NH-tert.butyl, R9means nitro, amino or a group with other10in which R10means the group COR11where R11denotes hydrogen, alkyl with 1-6 carbon atoms, or R8means amino, a R9- group-other10where R10has the specified value.

Thanks herbicide activity of the compounds of the above formula (I) (hereinafter: "the proposed connection") and their salts can be an active ingredient herbicide agent that is a further object of the invention. This tool contains an effective amount of the active substance.

Herbicide means may be in the form of any standard of drug, which has been created concentrates, emulsion as, for example, emulsions of the type oil in water or water in oil, spray solutions, suspendiruemye concentrates, dispersions based on oil or water mixed with oil solutions that are enclosed in capsules suspension, powered tools, treaters, sprinkle the granules, granules for application to soil, microgranules, spray granules, suspension granules and adsorption granules, water dispersible granules, preparations for distribution of the active substance in an extremely low volume, microcapsules and waxes. These preparations can contain auxiliary substances, such as inert substances, surfactants, solvents and further additives target.

On the basis of these preparations can be prepared mixtures of the proposed active substances with other pesticide chemicals, for example, insecticides, acaricides, other herbicides, fungicides, antidotes, fertilizers and/or plant growth regulators. Such combinational drugs can enter the trade in finished form or they can do in the tanks immediately before use.

Wettable powders are raunemaa contain more surfactants of ionic and/or nonionic type wetting (wetting, dispersants), for example, polyoxyethylene ALKYLPHENOLS, polyoxyethylene the fatty alcohols, polyoxyethylene fatty amines, sulfates simple polyglycolic ether of fatty alcohol series, alkanesulfonyl, alkylbenzenesulfonate, ligninsulfonate sodium, 2,2'-dynafilter-6,6'-desultorily sodium, di-butylnaphthalene-solitarily sodium or oleoylethanolamide sodium. To obtain a wettable powder herbicide active substance is finely pulverized in a conventional apparatus, for example, a hammer mill, air mill or mill with jet blower, and together with the grinding or after it is mixed with auxiliary substances.

Emulsifiable concentrates are obtained by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or high-boiling fragrances or hydrocarbons or mixtures of organic solvents, adding one or more surfactants of ionic or nonionic type (emulsifiers). As emulsifiers can be used, for example, alkylarylsulfonate calcium salt such as, for example, dodecylbenzenesulfonic alkylarylsulphonates ether, simple polyglycidyl ether of fatty alcohol series, condensation products of propylene oxide and ethylene, a simple alkylhalides, complex arbitarily ether as, for example, a complex arbitarily a fatty acid ester, or a complex polyoxyethylenesorbitan ether as, for example, a complex polyoxyethylenesorbitan ether fatty acids.

Powdered preparations are obtained by grinding the active substance with finely dispersed solids such as talc, natural clays, such as kaolin, bentonite or pyrophyllite, or diatomaceous earths.

Suspension concentrates may be water-based or oil. They can be obtained, for example, by wet grinding by means of commercially available mills, and if necessary, adding the above-mentioned surface-active substances.

Emulsion as, for example, emulsions of the type oil in water can be obtained, for example, with agitators, colloidal mills and/or static mixers using aqueous organic solvents and, if necessary, the above-mentioned surface-active substances.

The granules can be obtained either by spraying the active substance Nava by adhesives, as, for example, polyvinyl alcohol, polyacrylnitrile sodium, or mineral oils, to the surface of carriers such as sand, kaolinites or granulated inert material. In addition, suitable active substances can be pelletized famous for producing granular techniques, if necessary in a mixture with fertilizers.

Dispersible in water, the granules get generally customary methods, for example by spray drying, granulation in the fluidized bed, granulating plates, mixing using high-speed mixers or extrusion without the use of a solid inert material.

The agrochemical preparations normally contain 0.1 to 99 wt.%, in particular of 0.1 to 95 wt.% the active substance of the formula (I) or its salt.

The concentration of active substance in wettable powders is, for example, about 10 to 90 wt.%, and the balance to 100 wt.% consists of a conventional auxiliary substances. In emulsifiable concentrates, the concentration of the active substance may be about 1 to 90 wt.%, preferably 5 to 80 wt.%. Powdered preparations contain 1 to 30 wt.%, in most cases 5 to 20 weight. % of active substance, and rasbridge water granulates of the active substance partially depends on whether the active substance, solid or liquid, and the type of excipients, fillers, etc. In dispergiruyushchie in the water the granules, the active substance is, for example, 1 to 95 wt.%, preferably 10 to 80 wt.%.

In addition, the above-mentioned preparations can contain conventional adhesives, wetting, dispersing agents, emulsifying agents promoting penetration agents, preservatives, antifreeze agents, solvents, fillers, carriers and colorants, defoamers, retarding evaporation means and affect the pH and viscosity of the funds.

Known pesticides that can be applied in a mixture with the proposed active substances for the preparation of the above mentioned preparations or products obtained in the tanks immediately before use, as described, for example, in Weed Research 26, 441-445 (1986); "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91,, Bracknell, England, and the literature there.

Before using any of these drugs, for example, wettable powders, emulsifiable concentrates, dispersions and dispersible in water, the granules can be diluted with water of known techniques, and the resulting work drugs applied to plants, parts kotoroy they grow up or are in the form of seeds. Powdered medications applied to the soil granules or scatter the granules and spray solutions to use are usually not diluted with further inert substances.

The required rate of application of the proposed compounds depends on external conditions, such as temperature, humidity and the type of the applied herbicide. It can vary within wide limits, for example, from 0.001 to 10.0 kg/ha or more of active substance, however, preferably it ranges from 0.005 to 5 kg/ha.

Another object of the invention is a method of weed control by treatment of the latter or its habitat or plants, their seeds or planting areas proposed by the compounds of formula (I) or their salts in an effective amount.

Receipt of the proposed compounds of formula (I) is illustrated by the following examples.

Example 1

Methyl ester 2-amino-4-nitrobenzoic acid

A mixture of 118.8 g of 2-amino-4-nitrobenzoic acid, 1000 ml of methanol and 120 ml of concentrated sulfuric acid is heated to boiling for 16 hours. The mixture is condensed under reduced pressure, absorb in a complex ethyl ester of acetic acid and washed with saturated solution of bicarb the th ether 2-amino-4-nitrobenzoic acid; melting point: 156-158oC.

Example 2

Methyl ester 2-chlorosulfonyl-4-nitrobenzoic acid

To a suspension of 1300 ml of glacial acetic acid, 516 ml of concentrated hydrochloric acid and 441,7 g (1,689 mol) of a compound methyl ester 2-amino-4-nitrobenzoic acid obtained according to example 1, at a temperature of 13-15oC drops add a solution 122,3 g of sodium nitrite in 180 ml of water. Stir for 30 minutes, and then this reaction mixture drops at a temperature of about 26oC added to a solution of 17 g of copper chloride (II) and 1300 ml of glacial acetic acid saturated with sulfur dioxide. After the evolution of gas poured on ice water, the precipitated soulforged sucked off, washed with water, and drying receive 354,3 g complex methyl ester 2-chlorosulfonyl-4-nitrobenzoic acid; melting point: 88-90oC.

Example 3

N-tert.butyl-2-methoxycarbonyl-5-nitro-benzosulfimide

To a solution of 384 g of complex methyl ester 2-chlorosulfonyl-4-nitrobenzoic acid obtained according to example 2, in 1500 ml of ethyl acetate at a temperature of 0oC add drops 206 g of tert.of butylamine. Then the reaction mixture is allowed to warm to room temperature is th the organic phase is dried over magnesium sulfate and concentrated. The residue is thoroughly stirred with a simple diisopropyl ether. Get 377,6 g target sulfonamida; melting point: 122-124oC.

Example 4

g) N-tert.butyl-2-dimethylaminoethyl-5-nitro-benzosulfimide

115 g of N-tert.butyl-2-methoxycarbonyl-5-nitrobenzenesulfonamide obtained according to example 3, in 1500 ml of methanol injected approximately 200 g of dimethylamine gas. The resulting mixture was stirred at a temperature of approximately 35oC during the week. The solution is concentrated under reduced pressure, the residue is absorbed in ethyl acetate, and successively washed with diluted hydrochloric acid, saturated sodium bicarbonate solution and saturated sodium chloride solution. After drying over magnesium sulfate the organic phase is thickened. Obtain 92 g of N-tert. butyl-2 - dimethylaminoethyl-5-nitro-benzosulfimide; melting point: 138-141oC.

Example 5

5-Amino-N-tert.butyl-2-dimethylaminoethyl-benzosulfimide

To a suspension of 22.0 g of N-tert.butyl-2-dimethylaminoethyl-5-nitro-benzosulfimide obtained according to example 4 of 18.2 g of ammonium chloride, 70 ml of water and 150 ml of methanol add to 23.6 g of zinc powder. The resulting mixture was stirred at a temperature of 50oC. On t, the residue is absorbed in ethyl acetate and washed with water. After drying over magnesium sulfate the organic phase is concentrated, and the residue is washed simple diisopropyl ether. Get 17,5 g of target compound; melting point: 205-208oC.

Example 6

N-tert. butyl-2-dimethylaminoethyl-5 - methoxycarbonylamino-benzosulfimide

To a suspension of 1.50 g of 5-amino-N-tert.butyl-2-dimethylaminoethyl-benzosulfimide obtained according to example 5 and of 1.46 g of sodium bicarbonate in 50 ml of acetonitrile at a temperature of 0oC add drops of 0.47 g of a complex of methyl ether of Harborview acid. Upon completion of the reaction, the reaction mixture was absorbed in ethyl acetate, washed with 1 N. hydrochloric acid, dried over magnesium sulfate and concentrated. Obtain 1.48 g of N-tert.butyl-2 - dimethylaminoethyl-5-methoxycarbonylamino-benzosulfimide; melting point: 184-188oC.

Example 7

N-tert.butyl-2-dimethylaminoethyl-5-formylamino-benzosulfimide

A mixture of 0.34 ml of formic acid and 0.70 ml of acetic anhydride for 2 hours, heated at a temperature of 50oC, then add a solution of 0.85 g of 5-amino-N-tert.butyl-2-dimethylaminoethyl-benzosulfimide obtained according to note is diluted hydrochloric acid and saturated sodium bicarbonate solution. In the drying over magnesium sulfate and concentrating the organic phase obtain 0.88 g of a high-viscosity substance, which without further purification used for further reactions.

Example 8

N-tert.butyl-2-dimethylaminoethyl-5 - propionamido-benzosulfimide

0,85 g of 5-Amino-N-tert.butyl-2-dimethylaminoethyl-benzosulfimide obtained according to example 5, at a temperature of 0oC dissolved in 3.5 ml of dimethylformamide, and added 0.28 g of acid chloride of propionic acid and 0.50 ml of triethylamine. Stir for one hour at a temperature of 5oC drops, the mixture is then absorbed in ethyl acetate and successively washed with diluted hydrochloric acid and water. In the drying over magnesium sulfate and concentrating the organic phase gain of 0.60 g of highly viscous substances, which without further purification used for further reactions.

Example 9

2-Dimethylaminoethyl-5-methoxycarbonylamino - benzosulfimide

1.48 g of N-tert.butyl-2-dimethylaminoethyl-5-methoxycarbonylamino-benzosulfimide obtained according to example 6, are stirred in 25 ml triperoxonane acid for 18 hours. After the distillation of the acid residue is suspended in toluene. In the R>
2-Dimethylaminoethyl-5-formylamino-benzosulfimide

Analogously to example 9 of 0.85 g of N-tert.butyl-2-dimethylamino-carbonyl-5-formylamino-benzosulfimide obtained according to example 7, is subjected to the interaction with 10 ml triperoxonane acid. Obtain 0.88 g highly viscous mass, which without further purification used to perform the reaction in example 13.

Example 11

2-Dimethylaminoethyl-5-propionamido-benzosulfimide

Analogously to example 9 of 0.80 g of N-tert.butyl-2-dimethylamino-carbonyl-5-propionamido-benzosulfimide subjected to interaction with 10 ml triperoxonane acid. Get 0,80 g highly viscous mass, which without further purification used to perform the reaction in example 14.

Example 12

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-methoxycarbonylamino-benzosulfimide

To a suspension of 1.40 g of 2-dimethylaminoethyl-5-methoxycarbonylamino-benzene-sulfonamida obtained according to example 9, and 1.28 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine in 30 ml of acetonitrile at a temperature of 0oC drops add diazabicyclo. The temperature slowly give rise to room. After distillation, the new hydrochloric acid, and then released the sulfonylurea washed with methanol and simple diisopropyl ether, and then dried. Obtain 1.45 g of the target compound as a colorless solid; melting point: 181-182oC (decomposition).

Example 13

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylamino-carbonyl-5-formylamino-benzosulfimide

Analogously to example 12 0.88 g of 2-dimethylaminoethyl-5-formylamino-benzosulfimide obtained according to example 10, is subjected to the interaction with 0,89 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine and 0.98 g of diazabicyclo in 10 ml of acetonitrile. Get 0,69 g of crystalline sulfonylureas; melting point: 126-127oC (decomposition).

Example 14

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-propionamido-benzosulfimide

Analogously to example 12 0,80 g 2-dimethylaminoethyl-5 - propionamido-benzosulfimide subjected to interaction with 0.74 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine and 0.82 g of diazabicyclo in 10 ml of acetonitrile. Gain of 0.68 g of crystalline sulfonylureas; melting point: 135-140oC (decomposition).

Example 15

N-[(4,6-dimethoxypyrimidine-2-yl>To a mixture of 0.93 g of N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-2-dimethylaminoethyl-5-methoxycarbonylamino-benzosulfimide in 20 ml of acetonitrile add to 1.85 ml of 1 N. sodium lye. After a clear solution is formed, the mixture is condensed under reduced pressure. The residue is stirred with a small amount of simple diisopropyl ether. Get 0,82 g target salt; melting point: 187-191oC (decomposition).

Example 16

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-formylamino-benzosulfimide in the form of sodium salt

Analogously to example 15 interaction is subjected to 0.30 g of N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-2-dimethylaminoethyl-5-formylamino-benzosulfimide obtained according to example 13, and 0.65 ml of 1 N. sodium liquor in 4 ml of methanol and 4 ml of dichloromethane. Obtain 0.32 g of the above sodium salt; melting point: 205oC (decomposition).

Example 17

N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-propionamido-benzosulfimide in the form of sodium salt

Analogously to example 15 interaction is subjected to 0.30 g of N-[(4,6-dimeth-oxopyrrolidin-2-yl)-aminocarbonyl] -2-dimethylaminoethyl-5-propionamido-Ben is and. Obtain 0.31 g of the above sodium salt; melting point: 212oC (decomposition).

Analogously to examples 12 to 17 get the compounds of formula (I), summarized in table 1.

Examples

(a) Powdered drug get due to the fact that 10 weight.parts of the compound of example 12 are mixed with 90 weight.parts of talc as inert substance, and the resulting mixture is ground in an impact mill.

b) Legalisierung in water, wettable powder is due to the fact that 25 weight. parts of the compound of example 13 is mixed with 64 weight.parts containing kaolin quartz as inert substance, 10 weight.parts ligninsulfonate potassium and 1 weight part oleoylethanolamide sodium as wetting agent and dispersant, and the resulting mixture was ground in a rod mill.

in) Legalisierung in water dispersion concentrate get due to the fact that 20 weight. parts of the compound of example 45 is mixed with 6 weight.parts simple alkylphenol ether (trade product Triton X 207), 3 weight. parts simple isotridekanolethoxylate ether (containing 8 mol of ethylene oxide) and 71 weight.part of paraffinic mineral oil (boiling within about 255 to above 277o

d) Dispersible in water granulate get due to the fact that 75 weight. parts of the compound of example 56 is mixed with 10 weight.parts ligninsulfonate calcium, 5 weight.parts of lauryl sodium, 3 weight.parts of polyvinyl alcohol and 7 weight. parts of kaolin, the resulting mixture is pulverized using a rod mill, and the powder granularit in the fluidized bed by injecting water into it.

e) Dispersible in water, the granules are also due to the fact that in a colloidal mill homogenized and pre-milled mixture of 25 weight. parts of the compound of example 57, 13, 5 weight.parts of 2,2'- dynafilter-6,6'-disulfonic sodium, 2 weight.parts alarmlistener sodium, 1 weight. part of polyvinyl alcohol, 17 weight.parts of calcium carbonate and 50 weight.parts of water. Then carry out the grinding to the desired size of the particles, and the resulting suspension is sprayed and dried in the spray tower, equipped with a single nozzle.

Herbicide activity proposed compounds is illustrated by the results of the following experiments.

Experience AND

The effect on the weeds in R is th clay soil in plastic pots, and then on the ground put the covering layer of the same land. Available in the form of a wettable powder or emulsion concentrate of the active substance is diluted with water, taken in an amount of 600 - 800 g/ha of the resulting aqueous suspension or emulsion is applied to the top surface of the soil in different doses indicated in tables 2, 3.

After treatment, the pots are placed in a greenhouse and allowed to stand there in terms of weed growth. Optical assessment of damage to the plants is carried out after the shoot experimental plants after 3 to 4 weeks compared to untreated control plants.

Active ingredients and their percentage herbicide action are summarized in tables 2, 3.

Experience B

The effect on the weeds in the post-harvest processing

Seeds or isomnia pieces of mono - and decotigny weeds contribute in sandy clay soil in plastic pots, and then on the ground put the covering layer of the same land. The pots are placed in a greenhouse under conditions of growth of the weeds. Three weeks after sowing the test plants in the stage of development of the three leaves, treated with herbicide.

Available as a wettable powder or emulsion contenty applied to the green parts of plants in different doses specified in tables 4 - 7. After 3 to 4 weeks of growing test plants in the greenhouse under optimal conditions determine the optical activity of drugs in comparison with untreated control plants.

The active substance and interest herbicide action are summarized in tables 4 - 6.

The experience IN

Tolerance to herbicides cultivated plants

For these experiments the seeds of a number of cultural and wild plants sown in a sandy clay soil, which is covered with a layer of the same land. Part of the pots immediately treated according to the above item 1, and the remaining pots are placed in a greenhouse until the development of two or three true leaves of plants and then the plants are treated with herbicides applied at different doses is shown in table 7. After 4 to 5 weeks after treatment and stay in the greenhouse optical determine herbicide activity and tolerability. The active substance and interest rate data for these two indicators are summarized in table 7.

In experiments And In use well-known of these nearest analogue of compounds I - IV formula

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where the radicals have the meanings shown in table A.

Sravanbelgola action and selectivity of action, than known compounds of similar structure,

The compounds of examples 14 - 69 exhibit similar properties.

1. The acylated aminophenylacetylene General formula

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where R1and R2is hydrogen or alkyl with 1 or 2 carbon atoms or together with the nitrogen atom to which they are linked, form a heterocyclic ring with 3 to 8 ring atoms;

R3group-COR5where R5means hydrogen, alkoxy with 1 to 4 carbon atoms, alkyl with 1 to 6 carbon atoms which may be substituted in the alkyl part 1 to 3 halogen atoms, cycloalkyl with 3 to 8 carbon atoms, mono - or dialkylamino with 1 to 4 carbon atoms in each alkyl part, the group-NH-R6where R6means pyrimidine ring, unsubstituted or substituted two CNS groups with 1 to 4 carbon atoms, or-SO2R7where R7has the meaning of the radical R5except alkoxy with 1 to 4 carbon atoms;

R4is hydrogen, alkyl with 1 to 4 carbon atoms;

X, Y is halogen, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, mono - or dialkylamino from 1 to 14 carbon atoms in each alkyl part;

Z is CH or N,

or their salts.

2. Acylated aminophenylacetic heterocyclic ring with 4 - 8 ring atoms, or their salts.

3. The acylated aminophenylacetylene General formula I on p. 1, where X and Y denote halogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, or their salts.

4. The acylated aminophenylacetylene General formula I on p. 1, where R1and R2together with the nitrogen atom to which they are linked, form a heterocyclic ring with 5 or 6 ring atoms; R3group-COR5where R5denotes hydrogen, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms which may be substituted in the alkyl part 1 to 3 halogen atoms, cycloalkyl with 3 to 6 carbon atoms, mono - or dialkylamino with 1 to 4 carbon atoms in each alkyl part, or group-SO2R7where R7means alkyl with 1 to 3 carbon atoms which may be substituted by 1 to 3 halogen atoms; R4is hydrogen, methyl; X, Y is halogen, alkyl with 1 to 2 carbon atoms, alkoxy with 1 to 2 carbon atoms, or their salts.

5. Derivatives phenylsulfonyl General formula XVI

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where R1and R2are specified in the PP.1 - 4 values;

R8and R9have the following meaning: if R8means a group NH-tert.butyl, R9means of NITR the keel 1 6 carbon atoms, or R8means amino, and R9- group-other10where R10has the specified value,

representing intermediate products to obtain the acylated aminophenylacetylene General formula I on PP.1 to 4.

6. Herbicide remedy containing the active substance on the basis of acidified aminophenylacetylene and target additives, characterized in that as acylated aminophenylacetylene it contains compounds of General formula I on PP.1 - 4 or its salt in an effective amount.

7. Method of weed control by treatment of the latter or its habitat or plants, seeds or planting areas acylated by aminophenylacetylene, characterized in that as the acylated aminophenylacetylene use of compounds of General formula I on PP.1 - 4 or its salt in an effective amount.

 

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