Derivatives of acylated aminophenylacetylene and method of production thereof

 

(57) Abstract:

Describes acylated derivatives of aminophenylacetylene General formula I, where the values of G, Y, X, Z specified in paragraph 1 of the claims, and their alkali metal salts. They can be used as herbicides for the selective control of weeds in cultivated plants. Describes how they are received. 2 S. and 2 C.p. f-crystals, 3 PL.

The invention relates to the technical field of herbicides and plant growth regulators, in particular of herbicides for selective control of weeds in cultivated plants.

It is known that geterotsiklicheskikh substituted phenylsulfonylacetate with the phenyl ring of the amino group or functionalized with an amino group, possess herbicide and regulating plant growth properties (see application EP No. 115 and 116518; US patents N 4892946; 4981509, 4664695 and 4632695).

Object of the invention is the expansion of the range of derivatives aminophenylacetylene possessing biological activity, in particular herbicide activity.

The problem is solved acylated derivatives of aminophenylacetylene total FR>2the following formulas

< / BR>
R is a residue of the formula CO2R5where R5means alkyl with 1-5 carbon atoms, R1-alkyl with 1-5 carbon atoms,

R2- CO2-alkyl with 1-5 carbon atoms,

R3is hydrogen, alkyl with 1-5 carbon atoms,

R4- formyl or CO alkyl with 1-5 carbon atoms, CO2-alkyl with 1-5 carbon atoms, unsubstituted or substituted by one or more Halogens, SO2is alkyl with 1-4 carbon atoms, CO-other6where R6is alkyl with 1-4 carbon atoms, or CSNHR7where R7is alkyl with 1-4 carbon atoms,

X - alkoxyl with 1-2 carbon atoms or dialkylamino with 1-2 carbon atoms in each alkyl part,

Y is halogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms or haloalkoxy with 1 or 2 carbon atoms,

X is a CH group or nitrogen,

or their alkali metal salts.

The first group preferred acylated derivatives of aminophenylacetylene General formula (I) include compounds in which

G is a radical of formula (G1)

R is a residue of the formula CO2R5where R5means alkyl with 1-4 carbon atoms,

R1is alkyl with 1-4 carbon atoms,

R2group SoH metals. The second group preferred acylated derivatives of aminophenylacetylene General formula (I) include compounds in which

G is a radical of formula (G2)

R - group CO2R5where R5means alkyl with 1-5 carbon atoms,

R3is hydrogen, alkyl with 1-4 carbon atoms,

R4-formyl, CO-alkyl with 1-4 carbon atoms, CO2is alkyl with 1-4 carbon atoms, SO2is alkyl with 1-4 carbon atoms, CO-other6where R6means alkyl with 1-4 carbon atoms,

X, Y and Z have the indicated meaning, and their alkali metal salts.

A further object of the present invention is a method of obtaining the proposed compounds of formula (I) or their salts of alkali metals, which consists in the fact that the compound of formula (II)

< / BR>
where R, R1, R2have the above meaning,

subjected to interaction with a heterocyclic carbamate of formula (III),

< / BR>
where X and Y have the above significance, a R*means unsubstituted or substituted phenyl or alkyl with 1-4 carbon atoms, with subsequent isolation of the target product in free form or in the form of salts of alkali metals.

The reaction of compounds of formulas (II) and (III) predpochtitelnei, as, for example, dichloromethane, acetonitrile, dioxane or tetrahydrofuran, at temperatures from -10oC to the boiling point of the respective solvent. The grounds are used, for example, organic aminoaniline, such as, for example, 1,8-diaza-bicyclo[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 (III) can be obtained, for example, the following method.

On the basis of the compounds of formula (IV), for example, 2-methyl-4-nitrobenzenesulfonyl, oxidation of the methyl group of suitable oxidizing agents such as potassium permanganate, lead to the corresponding carboxylic acids [similar to the method in Org. Syn. Coil., volume 3, 740 (1955)], which esterification of the corresponding alcohols R5-OH in the presence of acid catalyst was transferred to esters of the formula (V), which is represented by scheme 1 (see Tetrahedron, 36, 2409 (1980)).

Circuit 1

< / BR>
Sulfonic acids (V) can be converted to N-tert-butylsulfonyl (VI) known standard methods. So, for example, potassium salts of sulfonic acids (V) are subjected to interaction with phosphoroxychloride or thionyl chloride in the absence or in the environment of a trade is ω (see Hosenball-Klamann, "Methods der organischen Chemie", 4-oe edition, volume E XI/2, pages 1067-1073, Thieme publishing house, , Stuttgart, DE, 1985). The resulting sulfochloride transfer interaction with tert-butylamine in the sulfonamides of the formula (VI) (see scheme 2). This reaction is carried out usually at temperatures of from -78oC to +80oC, preferably from 0 to 30oC in solvents such as, for example, dichloromethane, trichloromethane, tetrahydrofuran, dioxane, methanol or ethanol.

Scheme 2

< / BR>
The nitro-group in the compound of formula (VI) is then transferred to the amino group (see scheme 3).

Recovery can be accomplished, for example, with hydrogen in the presence of a catalyst such as palladium or iron in acetic acid environment (see H. berry, T. Neuhold, F. S. spring, And hem. The juice. 1952, 2042; M Freifelder, "Catalytic Hydrogenation in Organic Synthesis: Procedures and Commentary, ed. J. The Wylie and Dignity, new York (1978), Chapter 5).

Scheme 3

< / BR>
The resulting anilines of the formula (VII) is subjected to derivatization at the amino group by monoalkylamines with subsequent acylation (see diagram 4).

Scheme 4

< / BR>
Monoalkylamines amino compounds (VII) can be easily realized by the method of C. Krishnamurti [Tetrahedron Lett. 23, 3315 (1982)]. Usainbolt, isocyanates, thioisocyanate, sulfochloride, amidosulfuric to N-acylated compound (VIII) can be likewise known from the literature (see A. L. J. Smith. Benicar and j. Zabicki, "The Chemistry of Amides", pages 73-185, ed. Entertains, New York, 1970; E. DF. Korah and others, "Tetrahedron Lett. 1978, 1051: H. J. Saunders, P. J. Slocomb, Chem. Rev. 43, 203 (1948): N Ozaki, Chem. Rev. 72, 457, 469 (1972): j. Solis, Arzneim.-Forsch. 33, 2 (1983); Houben - Weyl-Hagemann, Methods der organioschen Chemie", 4th ed., volume E 4, page 282, publisher Thieme Verlag, , Stuttgart, DE, 1983; J. Galinski, M. Majocha, Synthesis 1978, 823; Houben-Weyl-Muller, "Methods der organischen Chemie", 4th edition, volume IX, pages 338 - 400 and 505 - 622, publisher Thieme Verlag, , Stuttgart, DE, 1955; Houben-Weyl-Klamann, Methods der organischen Chemie", 4th edition, volume EII/2, page 1020 - 22, Thieme publishing house Verlag, , Stuttgart, DE, 1985). Cleavage of the tert-butyl groups of the compounds of the formula (VIII) to obtain the sulfonamides (II) carry out, for example, strong acids according to the following scheme 5.

Scheme 5

< / BR>
As strong acids are used, for example, mineral acids, such as sulfuric acid or hydrochloric acid, or strong organic acids, such as, for example, triperoxonane acid. The reaction is carried out, for example, at temperatures between -20 and with whom I such as, for example, dichloromethane or trichloromethane. But the reaction can also be carried out in the absence of solvent.

Another method of preparing compounds (II) represented by the following scheme 6.

In amino-nitrotoluene formula (IX), for example, 3-amino-2-methyl-nitrobenzene enter the substituents R1and R2or R3and R4by monoalkylamines and acylation (similar to the scheme 4). Thus obtained compound (X) is subjected to oxidation, for example, potassium permanganate (similar to scheme 1). The resulting derivatives of benzoic acid is subjected to the esterification of known standard methods (similar to scheme 1). The resulting aromatic esters (XI) can be restored to the anilines of the formula (XII) (similar to scheme 3). After the diazotization of anilines (XII) and subsequent interaction with the sulfur dioxide receive sulfochloride (XIII) (see Houben-Weyl-Muller, "Methods der organischen Chemie", 4th edition, volume IX, pages 563 and following, publisher Thieme Verlag, Stuttgart, DE, 1955).

The ammonolysis of sulfochloride (XIII) leads to the sulfonamides (II). This reaction is carried out, for example, at temperatures from 0 to 40oC in the presence of organic solvents, such as, for example, BR> An alternative way of obtaining sulfochloride (XIII) is represented in the diagram below, 7.

Nitrobenzoic acid of the formula (XIV), such as, for example, 2-chloro-3-nitro - or 2-chloro-5-nitrobenzoic acid, after esterification (similar to scheme 1, step 2) turn to the sulphides of the formula (XV) by interaction with a suitable salt of the mercaptan at temperatures from 0 to 80oC in inert solvents, such as, for example, acetonitrile, methanol or ethanol. As salts of mercaptans suitable, for example, sodium or potassium salt of benzylmercaptan. After the restoration of the nitro group of compound (XV), as well as the introduction of substituents R1and R2or R3and R4(similarly, figure 4), the compound of formula (XVI) is subjected to interaction with chlorine or hypochlorite in oxidizing conditions to receive sulphonylchloride (XIII) (see, for example, R. T. Langer, Can. J. Chem. 54, 498 (1976); reference Houben-Weyl-Muller, "Methods der organischen Chemie", 4th edition, volume 9, pages 580 - 583, publisher Thieme Verlag, , Stuttgart, 1955). This reaction is carried out at temperatures from -10 to 60oC, preferably from 0 to 15oC, in the two-phase system. As the aqueous phase is suitable, for example, water, phosphate buffer solutions (pH 7) or Required to interact with the compounds (II) carbamates of the formula (III) are known from the literature or can be obtained analogously to known methods.

Alkali metal salts of compounds of formula (I) preferably get in inert solvents, such as, for example, water, methanol, acetone, dichloromethane, tetrahydrofuran, toluene or heptane, at a temperature from 0 to 100oC.

The proposed compounds of formula (I) or their salts have a very good herbicide activity against a wide range of important from an economic point of view, mono - or doctrine weeds.

Offer active substances are also well suited to combat trudnookislyaemymi perennial weeds that sprout from the rhizome, roots or other perennial organs. If this is not important if they use substances before sowing, before or after the shoot. If this can be called, for example, some representatives of the mono - and dicotyles weeds, which destroyed the proposed compounds (listed in no case is not a limitation destroying offer connections weeds).

The compounds of formula (I) or their salts can be translated in various preparations depending on the biological and/or chemico-physical parameters. Such preparations can be, for example: macii, as, for example, emulsions of tipov oil in water and water in oil, spray solutions, suspension concentrates, dispersions based on oil or water mixed with oil solutions that are enclosed in capsules, suspensions, treaters, sprinkle the granules, granules for application to soil, microgranules, spray granules, suspension granules and adsorption granules, water dispersible granules, water-soluble granules, preparations for distribution of the active substance in an extremely low volume, microcapsules and waxes. These types of drugs are widely known and are described, for example, in the reference Winnacker-Kuhler, "Chemische Technologie", volume 7, publisher K. Hauser Verlag, , Munich, 4th edition 1986, DE; vada fan Walken-Burg, "Pesticide Formulations", ed. Marcel Dekker, , new York, 1973; K. Martin, "Spray Drying" Handbook, 3rd edition, 1979, US: Univ. G. Goodwin Ltd., , London, GB.

Before using any of these drugs, for example, wettable powders, emulsifiable concentrates, dispersions and dispersible in water, the granules can be diluted with water by known methods, for example, and the resulting work drugs applied to plants, parts of plants or to the soil in which they grow ages, as well as the spray solution before the application is usually not diluted with further inert substances.

The flow rate of the compounds of formula (I) depends on external conditions, such as, for example, temperature, humidity and the type of herbicide. It can vary within wide limits, for example from 0.01 to 10.0 kg/ha or more of active substance, but preferably it ranges from 0.005 to 5 kg/ha.

A. Chemical examples

a) methyl ester of 2-chloro-3-nitrobenzoic acid

is 25.50 g (to 0.127 mol) of 2-Chloro-3-nitrobenzoic acid are dissolved in 50 ml of methanol and mixed with 3 ml of concentrated sulfuric koloti. The reaction mixture is heated to boiling for 4 hours. After adding 10 ml of complex trimethylboron ether octoxynol acid mixture is then boiled for two hours.

After cooling to a temperature of 0oC and the extraction of the solids gain of 26.4 g (96%) of colorless complex methyl ester 2-chloro-3-nitrobenzoic acid c melting point 68 - 70oC.

b) methyl ester of 2-benzylmercaptan-3-nitrobenzoic acid

To a mixture of 50.0 g (0.23 mol) of a compound methyl ester 2-chloro-3-nitrobenzoic acid and 28,81 g (0.23 mol) of benzilic stirring at room temperature and stand for a further 15 hours, the reaction mixture is thickened. The residue is mixed with ethyl acetate and sequentially washed with saturated sodium bicarbonate solution, water and saturated sodium chloride solution. After drying over magnesium sulfate the solution is concentrated under reduced pressure. Yellowish oily residue (68,5 g; 97% of theory) is used without further purification in the next stage.

C) methyl ester of 3-amino-2-benzylmercaptan-benzoic acid

To the mixture 68,0 g (0.22 mol) of a compound methyl ester 2 - benzylmercaptan-3-nitrobenzoic acid, 215 ml of glacial acetic acid and 480 ml of water are added in several portions of 69.9 g of iron powder. Then the reaction mixture is stirred at a temperature of 50 - 60oC for three hours. After separation of the solids by filtration, the mother liquor is washed with water and brine and then dried over magnesium sulfate. After concentration of the solution under reduced pressure get to 47.1 g of yellow oil (77%);

1H-NMR (CDCl380MHz); = 3.8 (s, 3H, OCH3) a 3.9 (s, 2H, SCH2the dryer) and 5.9 (s, 2H, NH2), of 6.6 to 7.3 (m, 8H, Harene).

d) methyl ester of 2-benzylmercaptan-3-formylamino - benzoic acid

At a temperature of 0oC to 48.6 g (0,476 mol) of acetic anhydride precipitat to a temperature of 0oC and mixed with a solution of 50.0 g (0,183 mol) of a compound methyl ester 3-amino-2-benzylmercaptan-benzoic acid in 150 ml of tetrahydrofuran. Then the reaction solution was stirred at room temperature for 3 hours. The mixture is condensed under reduced pressure (60oC, 0.1 Torr). The resulting oily residue (61,77 g) used in the next stage without further purification.

d) methyl ester of 2-benzylmercaptan-3-methylamino-benzoic acid

To a solution of 61.5 g complex methyl ester 2-benzylmercaptan-3-formulainvesting acid (see phase g) in 100 ml of chloroform was added dropwise at a temperature of 0oC 20 ml brandimensions. Then heated to a temperature of 60oC for 2 hours, add a further 20 ml of brandimensions and the mixture is stirred at the same temperature for 2.5 hours. Then added dropwise at a temperature of 0oC 30 ml of methanol. The mixture transferred to a separating funnel, washed with water and brine and then dried over magnesium sulfate. After distillation of the volatile components get 54,60 g complex methyl ester 2-benzylmercaptan-3-methylamino-benzoic acid in the form of a yellowish oil;

1H-NMR (CDCl3, 80 MHz): = 2,6 (d, 3H, NH-CH3arene.).

e) methyl ester 2-benzylmercaptan-3-(N-methoxycarbonylmethylene)-benzoic acid

To a suspension of 15.0 g (0,052 mol) of a compound methyl ester 2-benzylmercaptan-3-methylamino-benzoic acid and 5,88 g (0.07 mol) of sodium bicarbonate in 100 ml of acetonitrile was added dropwise to 4.6 ml complicated methyl ether of Harborview acid. After 5 hours distilled volatile components (15 Torr, 40oC). The residue is mixed with ethyl acetate and sequentially washed with 1 N. hydrochloric acid and water. After drying the organic phase over magnesium sulfate, the solvent is distilled off. Methyl ester 2-benzylmercaptan-3-(N-methoxycarbonylmethylene)-benzoic acid is obtained as a yellowish oil (14.8 g);

1H-NMR (CDCl3, 80 MHz): = 3,0 (s, 3H, N-CH3), and 3.6 (s, 3H, O-CH3) a 3.9 (s, 5H, OCH3and SCH2Hairdryer), a 7.1 to 7.6 (m, Harene).

f) methyl ester 2-chlorosulfonyl-3-(N-methoxycarbonyl - methylamino)-benzoic acid

The mixture 8,10 g complex methyl ester 2-benzylmercaptan-3-(N-methoxycarbonylmethylene)-benzoic acid in 50 ml of methylene chloride and 150 ml of primary phosphate, potassium secondary phosphate disodium (a product of the company Ricalde Jean Argon to remove excess chlorine. After phase separation the organic phase is dried over magnesium sulfate and then concentrated under reduced pressure. By crystallization from a mixture of ethyl acetate and hexane obtain 4.5 g of complex methyl ester 2-chlorosulfonyl-3-(N-methoxycarbonyl - methylamino)-benzoic acid. The melting point is 102-105oC.

C) N-[(4-dimethylamino-6-triptoreline-triazine-2-yl)-aminocarbonyl]- 2-methoxycarbonyl-6-(N-methoxycarbonyl-methylamino)-benzosulfimide (see table 1, example 3)

To a suspension of 0.25 g (0,0038 mol) of sodium cyanate, 0.6 ml of pyridine and 12 ml of acetonitrile successively added at room temperature 0.71 g (of 0.003 mol) 2-amino-4-dimethylamino-6-(2,2,2 - triptoreline)-triazine and 1.0 g (of 0.003 mol) of a compound methyl ester 2-chlorosulfonyl-3-(N-methoxycarbonyl-methylamino)-benzoic acid. After stirring at room temperature for 3.5 hours the reaction mixture is poured on ice water. For purification of the reaction product osadovskaya sulfonyl-urea stir in a small amount of methanol, separated by filtration and dried. The sulfonylurea is obtained as a colorless solid (0.75 g). The melting point is 125 - 126oC.

and) N-[(4,6-dimethoxypyrimidine-2-)

To a suspension of 0.61 g of sodium cyanate, 0.8 ml of pyrimidine and 18 ml of acetonitrile successively added at room temperature of 0.54 g of 2 - amino-4,6-dimethoxypyrimidine and 1.50 g of complex methyl ester 2-chlorosulfonyl-3-(N-methoxycarbonylmethylene)-benzoic acid. After stirring at room temperature for 3.5 hours the reaction mixture is poured on ice water. For purification of the reaction product osadovskaya the sulfonylurea stir in a small amount of methanol, separated by filtration and dried. Thus obtained N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-methoxycarbonyl-6-(N - methoxycarbonyl-methylamino)-benzosulfimide there as a colorless solid (1.35 g). The melting point is 150 - 154oC.

K) N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl]-2 - methoxycarbonyl-4-(N-methoxycarbonyl-methylamino)-benzosulfimide (see table 2, example 4)

To a mixture of 0.87 g of 2-methoxycarbonyl-4-(N-methoxycarbonylmethylene)- benzosulfimide and 0.90 g of 4,6-dimethoxy-2-phenoxycarbonylamino-pyrimidine in 10 ml of acetonitrile was added dropwise at a temperature of 0oC 0.6 ml of 1,8 - diazabicyclo[5.4.0] -undec-7-ene. Then the reaction solution was stirred at room temperaturedisplay the aqueous phase with concentrated hydrochloric acid (pH 1) osadovskaya the sulfonylurea stir in a small amount of methanol. After separation of a colorless solid by filtration and drying obtain 1.18 g of N-[(4,6-dimethoxypyrimidine-2-yl)-aminocarbonyl] -2-methoxycarbonyl-4-(N - methoxycarbonyl-methylamino)-benzosulfimide. The melting point is 184 - 186oC (decomp. ). This stage is repeated with the difference that the use of 31.8 g of benzosulfimide, 58,0 g pyrimidine, 150 ml of acetonitrile and 39.4 ml of 1,8-diazabicyclo [5.4.0]-undec-7-ene. After reaction at room temperature for 4 hours and processing get the reaction mixture of 45.0 g of product with a melting point of 187 - 189oC.

l) Sodium salt of N-[(4,6-dimethoxy-pyrimidine-2-yl)-aminocarbonyl]-2 - methoxycarbonyl-4-(N-methoxycarbonyl-methylamino)benzosulfimide (see table 3, example 1)

of 0.53 g of N-[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl] -2 - methoxycarbonyl-4-(N-methoxycarbonyl-methylamino)-benzosulfimide stirred in 50 ml of methylene chloride and 30 ml of acetonitrile, and then mixed with 1.1 ml of 1 N. sodium lye. After stirring for 2 hours the reaction solution is concentrated under reduced pressure (50oC, 0.1 Torr). Colorless salt (0,59 g) occurs as colorless solid. The melting point is 155 - 158oC. When ispalindrome liquor obtain 16.2 g of product with a melting point of 166oC (decomp.).

Summarized in the following tables 1 to 3 connections receive according to or analogously to examples h) - l).

Used in the following tables abbreviations:

So pl. = melting point

Et = ethyl

Me = methyl

nPr = n-propyl

various spare parts. = decomposition

B Examples of obtaining drugs

(a) Powdered drug get due to the fact that 10 weight. parts of the compounds of formula (I) is 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 compounds of formula (I) is mixed with 64 weight. parts containing kaolin quartz as inert substance, 10 weight. parts ligninsulfonate potassium and 1 weight. part alarmlistener 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 compounds of formula (I) is mixed with 6 weight. parts simple alkylphenol ether (trade product Triton X 207), 3 weight. parts simple isotridekanoletoxylate about 255 - over 277oC) and the resulting mixture is ground in a ball mill until a particle size below 5 microns.

g) Emulsifiable concentrate is obtained from 15 weight. parts of the compounds of formula (I), 75 weight. parts of cyclohexanone as solvent and 10 weight. parts atsetilirovanie of Nonylphenol as emulsifier.

d) Dispersible in water granulate get due to the fact that 75 weight. parts of the compounds of formula (I) is mixed with 10 weight. parts ligninsulfonate calcium, 5 weight. parts of lauryl sodium and 3 weight. parts of kaolin, the resulting mixture is pulverized using a rod mill and 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 compounds of formula (I), 5 weight. parts of 2,2'-dynafilter-6,6'- disulfonic sodium, 2 weight. parts alarmlistener sodium, 1 weight. part of polyvinyl alcohol 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.

C. Biological pilnik weeds contribute in sandy 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.

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 in 3-4 weeks by comparison with untreated control plants. As the results of the experiments, the proposed compounds exhibit good herbicide activity against a broad spectrum of weed grasses and plants. So, for example, at a flow rate of 0.3 kg and less of active substance per hectare connection examples 1.1 - 1.3, 2.1 -2.16, 3.1 - 3.7, shown in tables 1 to 3, show a very good herbicide activity against such weeds, such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli and Lolium Polygonum, which are subjected to a pre-emergence treatment.

2. The effect on the weeds after they shadowey processing

Seeds or isomnia pieces of mono - and decotigny weeds contribute in sandy clay soil in plastic pots and then put on after sowing the test plants, in the stage of development of the three leaves, treated with herbicide.

Available as a wettable powder or emulsion concentrate of the active substance is diluted with water, taken in the amount of 600 to 800 l/ha Obtained in this work drugs applied to the green parts of plants in different doses. After 3-4 weeks of growing test plants in the greenhouse under optimal conditions determine the optical activity of drugs in comparison with untreated control plants. And during post-harvest processing of the proposed tools are good herbicide activity against a wide range of important from an economic point of view weeds and plants. So, for example, at a flow rate of 0.3 kg and less of active substance per hectare connection examples 1.1 - 1.3, 2.1 -2.16, 3.1 - 3.7, shown in tables 1 to 3 show a good herbicide activity against weeds, such as, for example, Sinapis alba, Stellaria media, Echinochloa crus - galli, Lolium Polygonum, Chrysanthemum segetum and Avena sativa.

3. 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. H is x or three true leaves in plants, and then treated according to p. 2, with the compounds of formula (I) are used in various doses. After 4-5 weeks after treatment and stay in the greenhouse optical determine that pre-emergence and post-harvest processing of the proposed connection does not have any negative effects on dicotyledonous crops such as, for example, soybean, cotton, canola, sugar beets and potatoes, even if they are used in high doses. In addition, some compounds also have no negative effects on crop plants, such as barley, wheat, rye, millet type Sorghum, maize or rice. Thus, the compounds of formula (I) have a high selectivity for combating weeds in crops.

1. Derivatives of acylated aminophenylacetylene General formula I

< / BR>
where G - substituted N-acylaminoacyl selected from the group comprising residues G1and G2the following formula:

< / BR>
< / BR>
where R is the residue of the formula CO2R5where R5means alkyl with 1 to 5 carbon atoms;

R1is alkyl with 1 to 5 carbon atoms;

R2- CO2is alkyl with 1 to 5 carbon atoms;

R3is hydrogen, alkyl with 1 to 5 carbon atoms;2is alkyl with 1 to 4 carbon atoms, CO-other6where R6is alkyl with 1 to 4 carbon atoms, or CSNHR7where R7is alkyl with 1 to 4 carbon atoms;

X - alkoxy with 1 to 2 carbon atoms or dialkylamino with 1 to 2 carbon atoms in each alkyl part;

Y is halogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms or haloalkoxy with 1 or 2 carbon atoms;

Z is a CH group or nitrogen,

or their alkali metal salts.

2. Derivatives of acylated aminophenylacetylene formula I on p. 1, where G is the radical of formula (G1); R is the residue of the formula CO2R5where R5means alkyl with 1 to 4 carbon atoms; R1is alkyl with 1 to 4 carbon atoms; R2group CO2is alkyl with 1 to 5 carbon atoms; R3, R4X, Y and Z have the indicated meaning, and their alkali metal salts.

3. Derivatives of acylated aminophenylacetylene formula I on p. 1, where G is the radical of formula (G2); The R group CO2R5where R5means alkyl with 1 to 5 carbon atoms; R3is hydrogen, alkyl with 1 to 4 carbon atoms; R4- formyl, CO-alkyl with 1 to 4 carbon atoms, CO2is alkyl with 1 to 4 carbon atoms, SO2is alkyl with 1 to 4 carbon atoms, CO-other

4. The method of obtaining derivatives of acylated aminophenylacetylene formula I

< / BR>
where G - substituted N-acylaminoacyl selected from the group comprising residues G1and G2the following formula:

< / BR>
< / BR>
where R is the residue of the formula CO2R5where R5means alkyl with 1 to 5 carbon atoms;

R1is alkyl with 1 to 5 carbon atoms;

R2- CO2is alkyl with 1 to 5 carbon atoms;

R3is hydrogen, alkyl with 1 to 5 carbon atoms;

R4- formyl or CO alkyl with 1 to 5 carbon atoms, CO2is alkyl with 1 to 5 carbon atoms, unsubstituted or substituted by one or more Halogens, SO2is alkyl with 1 to 4 carbon atoms, CO-other6where R6is alkyl with 1 to 4 carbon atoms, or CSNHR7where R7is alkyl with 1 to 4 carbon atoms;

X - alkoxy with 1 to 2 carbon atoms or dialkylamino with 1 to 2 carbon atoms in each alkyl part;

Y is halogen, alkyl with 1 or 2 carbon atoms, alkoxy with 1 or 2 carbon atoms or haloalkoxy with 1 or 2 carbon atoms;

Z is a CH group or nitrogen,

characterized in that the compound of formula II

< / BR>
where R, R1, R2have the above values,

subjected to interaction with Kateriny or substituted phenyl or alkyl with 1 to 4 carbon atoms,

with subsequent isolation of the target product in free form or in the form of alkali metal salts.

 

Same patents:

The invention relates to an improved process for the preparation of substituted N-(1,3,5-triazine-2-yl)aminocarbonyl-arylsulfonamides General formula

< / BR>
where R1= Cl, COOCH3;

R2= OCH3N(CH3)2;

R3= CH3, ON=C(CH3)2, ON=C(CH3)C2H5;

R4= H, CH3,

used in agriculture as herbicides and plant growth regulators

The invention relates to the derived O-carbamidomethylation, specifically to methyl ether, 2-[[N-(4-methoxy-6-methyl-1,3,5-triazine-2-yl)-N-methylaminomethyl]aminosulfonyl]benzoi Noi acid of the formula I

< / BR>
have a weed-killing activity, and herbicide compositions based on it

Poroelasticity // 2047607
The invention relates to the sulfonylureas, in particular to new ferroelasticgadolinium General formula I:SO2NHNH(I) where R1-C4alkyl;

R1CH3CH2SP, CH2OCH3CH2OCH2CH3C1-C3alkoxy, CH2F, СНFCH3or CF2H;

X NHCH3or N(CH3)2provided that if R1is the co2CH3or CH2OCH3then R is different from the CH3that may find application in agriculture, as shown herbicide activity

The invention relates to new derivatives of phenylsulfonylacetate General formula I

where R is C1 (1A) or SOON3(1B), and their alkali and ammonium salts, which can find application in agriculture as herbicides and plant growth regulators

The invention relates to a new cyclopropylamino-1,3,5-triazines and their salts of General formula

< / BR>
in which R1- alkyl, cycloalkyl, alkylsilanes; R2bis (2-hydroxyethyl)amino, 3-hydroxy-1-azetidine, 3-methoxy-1-azetidine, 3-oxo-1-azetidine, morpholine-, 4-hydroxypiperidine, thiomorpholine-, S-oxide-thiomorpholine-, S, S-dioxide-thiomorpholine-, 3-thiazolidine, S-oxide-3-thiazolidine, S, S-dioxide-3-thiazolidine or 8-oxa-3-azabicyclo/3,2,1/ Oct-3-yl

The invention relates to chemical means of weed control in crops based on derivatives sulfonilmocevina, in particular salts of 2-chloro-N-/(4-methoxy-6-methyl-1,3,5-triazine-2-yl) aminocarbonyl/benzosulfimide(chlorsulfuron) and specifically to its potassium salt of formula I:

< / BR>
The invention relates also to a method of controlling undesirable vegetation in crops of flax by processing plants weed-killing drug on the basis of salts of formula I, as well as its mixture with other herbicide-active compounds, for example with dimethylamine salt of 2-methyl-4-chlorophenoxyacetic acid

The invention relates to a new derived arylsulfonyl-triethynylbenzene formula I

which can find application in agriculture as a herbicide for weed control in cereal crops and flax, as well as herbicide composition based on it

The invention relates to some 2,6-disubstituted pyridinium and 2,4-disubstituted the pyrimidines, the way they are received, to herbicide compositions on their basis and to a method of combating the growth of unwanted vegetation

The invention relates to a new method of obtaining 2-substituted 4,6-dialkoxybenzene General formula I

< / BR>
in which

R1and R2may be the same or different and mean (C1-C4)-alkyl, and R3means R4-O-, R4-S - or R4R5N-, where R4equal to C1-C4-alkyl, R5means a hydrogen atom, a C1-C4-alkyl or phenyl; 2-N-alkylamino-4,6-dimethoxypyrimidine and method for producing a halogen-substituted pyrimidine

Ammonium salts // 2106346

The invention relates to an improved process for the preparation of substituted N-(1,3,5-triazine-2-yl)aminocarbonyl-arylsulfonamides General formula

< / BR>
where R1= Cl, COOCH3;

R2= OCH3N(CH3)2;

R3= CH3, ON=C(CH3)2, ON=C(CH3)C2H5;

R4= H, CH3,

used in agriculture as herbicides and plant growth regulators

The invention relates to new derivatives of catechol and their pharmaceutically acceptable salts and esters which are useful as medicaments, antioxidants

The invention relates to new derivatives of sulfamethoxypyrazine and herbicides containing them as active ingredients
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