Aminothiazoline, methods for their preparation, herbicide composition, method for killing unwanted weeds

 

(57) Abstract:

Usage: in heterocyclic chemistry, as substances with herbicide activity. The inventive product-aminothiazoline F.-ly (1) where R1- halogen or galonsky alkyl; R2is lower alkyl or bromine; R3- (lower alkyl)carbonyl, (lower cycloalkyl)-carbonyl, (lower alkoxy) carbonyl or (lower alkyl) sulfonyl, which may be substituted with halogen, lower alkyl, lower alkoxy, R4- halogen, 2 method of producing compound (1), the intermediate connection F.-ly (2), the method of its production, herbicide composition based compounds (1) and a method of controlling weeds effective amount of the compound (1) (16 - 2000 g/ha).

7 C. and 12 C. p. F.-ly, 11 PL.

The invention concerns aminothiazoline, their preparation and use as herbicides and intermediates for their production. More specifically, it relates to compounds of aminothiazoline, with a strong herbicide action, and intermediate compounds for preparing compounds of aminothiazoline.

Known derivatives of aminothiazoline that can be used as the active ingredient of the herbicide rezultate was established, some compounds aminothiazoline have a strong herbicide action, and some of them also have significant selectivity between crops and weeds.

In accordance with the invention provides compounds of aminothiazoline formula

(1) in which R1halogen, halo/lowest/the alkyl, halo/lower/alkoxy or halo/lower/alkylthio;

R2lower alkyl, chlorine, bromine or iodine;

R3lower alkyl/carbonyl/low cycloalkyl/carbonyl/lower aloxi/carbonyl/lower cycloalkane/carbonyl/ or /lower alkyl/-sulfonyl,

all of which can be optionally substituted by the substituents, which may be identical or different and are selected from halogen, lower alkyl, lower alkoxy, lower cycloalkyl and lower cycloalkane;

R4is halogen, more specifically compounds aminothiazoline formula (1) in which R1is halogen, halo/C1-C3/by alkyl, halo/C1-C3/alkoxy or halo/C1-C3/ alkylthio; R2WITH1-C2the alkyl, chlorine, bromine or iodine; R3WITH1-C6alkylcarboxylic,3-C6cycloalkylcarbonyl,1- 1-C3of alkyl, C1-C3alkoxy, C3-C6cycloalkyl and C3-C6cycloalkane; R4is halogen compounds aminothiazoline formula:

R (IV) in which R1and R4each was defined above, and R6is hydrogen or stands, which are intermediate compounds for compounds (1); the method for obtaining compounds of aminothiazoline (IV), and herbicide composition containing as active ingredient the above-mentioned compounds aminothiazoline (1).

In accordance with the invention, the term Cn-Cmrefers to the number of carbons in the group, following immediately after this term. If, for example, WITH1-C6alkylcarboxylic term WITH1-C6specifies the number of carbons in the alkyl his part without regard to their number in its carbonyl parts. In addition, the group, substituted by the Deputy, in the preferred embodiment, includes a group bearing from 1 to 10 substituents, which may be identical or different.

Connection aminothiazoline (1) provides in General a strong herbicide daystudy on agricultural land, when processing the foliage or soil without any phyto-toxic action on crops.

Examples of broadleaf weeds include: garden purslane (Portulaca oleracea), woodlouse (Stellaria media), white pigweed (Chenopodium album), red pigweed (Amaranthus retroflexus), radish (Raphanus sativus) and mustard field (Sinapis arvensis), shepherd's-purse common (Capsella bursa-pastoris), hemp (Sesbania exaltata), wall-cress canadian (Cassia obtusifolia), limnocharis (Abutilon theophrasti), breast prickly Sida spinosa), violet field (Viola arvensis), cleaver (Galium aparine), morning glory plyuschevidnaya (Ipomoea hederacea), morning glory high (Ipomoea purpurea), field bindweed (Convolvulus arvensis), purple dead-nettle (Lamium purpureum), dead-nettle (Lamium amplexicaure), jimson weed (Datura stramonium), black nightshade (Solanum nigrum), Veronica foreign (Veronica persica), common cocklebur (Xanthium pensylvanicum), annual sunflower (Helianthus annuus), treherbert odorless (Matricaria perforata) and elative (Chrysanthemum segetum).

Examples of grass weeds include barnyard grass (Echinochloa frumentacea), plushie millet (Echinochloa crus-galli), green hermit (Setaria viridis), the hermit yellow (Setaria glauca), pearl millet (Digitaria ciliaris), weed blood (Digitaria sanguinalis), annual bluegrass (Poa annua), Alopecurus mirzahosseini (Alopecurus myosuroides), oats (Avena sativa), wild oat (Avena fatua), Rogovik unlovely (Sorgorum), cane field (Sorghum bicolor) and cynodon dactylon (Cynodon dactylon).

Some of the compounds of aminothiazoline (1) have the advantage that it does not cause any material damage to various crops, such as corn, wheat, barley, rice, soybeans, cotton, and sugar beets.

Connection aminothiazoline (1) is also effective in experiments in the fields against weeds, including grass weeds such as plushie millet (Echinochloa orysicola), broad-leaved weeds such as false full color (Lindernia procumbens), rotala Indian (Rotala indica), povoinik (Elatine triandra) and Ammania multifora), weeds of the family site such as umbel-like sedge (Cuperus difformis), cane forest (Scirpus juncoides), bolotnitsa coniferous (Eleocharis acicularis) and mustard field (Cyperus serotinus) and other weeds, such as odnolopastnoy (Monochoria vaginalis) and arrowhead (Sagittaria pygmaea). Some of the compounds of aminothiazoline (1) have the advantage that they do not possess the phytotoxicity relative to rice in the processing of irrigation water.

Among the compounds of aminothiazoline (1) preferred are those in which R1is the halo/C1-C3/by alkyl, preferably trifluoromethyl, those in which R2is stands ylcarbonyl, both can be optionally substituted by at least one Deputy, selected from halogen, C1-C3the alkyl and C1-C3alkoxy, and those in which R4contained in para-position, for example fluorine in the para-position.

Connection aminothiazoline (1) can be obtained using different procedures, examples of which are shown in schemes I-III.

Scheme I

< / BR>
Scheme II

< / BR>
Scheme III

R

where R1, R2, R3, R4and R6each was defined above, R7is (C1-C6alkyl)-carbonyl, R8and R9who are1-C6the alkyl, R10chlorine, bromine or iodine, and X and Y each is bromine or iodine.

Procedures for obtaining compounds of aminothiazoline (1), which presents the above schemes I-III, below is explained in detail.

Procedure (A).

Connection aminothiazoline (1) in which R2is stands or ethyl, can be obtained by the interaction of compounds of aminothiazoline (II) with a base or acid.

This reaction is in General carried out in a solvent at a temperature of from about 0 to 200about

The solvent can be mentioned aliphatic hydrocarbons (e.g. hexane, heptane), aromatic hydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diisopropyl simple ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl simple ether), alcohols (e.g. methanol, ethanol, isopropanol, tertiary butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol, glycerin), acid amides (e.g. N, N-dimethylformamide) and sulfur compounds (e.g., dimethylsulfoxide, sulfolan). These solvents may be used individually or in combination. Examples of bases are inorganic bases (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride) and an alkali metal alcoholate (e.g. sodium methylate, sodium ethylate, t-butyl potassium, t-butyl sodium). Examples of acids are sulfuric acid and hydrochloric acid.

After completion of the reaction, the reaction mixture can be subjected to standard post-processing on the place known techniques such as extraction with an organic solvent and concentration. If you want, then you can use any of the compound (I-I).

Procedure ().

Connection aminothiazoline (1) in which R2is stands or ethyl, can be obtained by the interaction of compounds aminothiazoline (IV) with an acid chloride (V) or anhydride of the acid (XIV) in the presence of a base, or by the interaction of compounds aminothiazoline (IV) acid (VI).

This reaction is in General carried out in a solvent at a temperature of from about 0 to 200aboutC for from 1 to 30 hours, the acid Chloride (V), the anhydride of the acid (XIV) or acid (VI) may be used in proportions of from 1 to 10 equivalents to one equivalent of the compound (IV), and the base may be used in proportions of from 1 to 50 equivalents to one equivalent of the compound (IV). If the reaction is carried out with the acid (VI), in the General case, use a condensing agent such as dicyclohexylcarbodiimide in the proportion of from 1 to 10 equivalents to one equivalent of the compound (IV).

The solvent can be illustrated by the following examples: aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbons (e.g. benzene, toluene, xylene, halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride is hostoi ether, dioxane, tetrahydrofuran, dietilen glycol dimethyl simple ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (for example, nitroethane, nitrobenzene), NITRILES (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N, N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. N, N-dimethylformamide) and sulfur compounds (e.g., dimethylsulfoxide, sulfolan). These solvents can be used singly or in combination. Examples of the base are organic bases (e.g. pyridine, triethylamine, N, N-diethylaniline) or inorganic bases (e.g. potassium carbonate, sodium hydroxide).

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that described in Procedure (A) to obtain the target compound (1), namely the compound (1-1).

Procedure C.

Connection aminothiazoline (1) in which R2is stands or ethyl, and R3is-CO-OR9can be obtained from vzaimodeistvie carried out in a solvent at a temperature of from about 10 to 200aboutC for 1 to 100 hours, the Alcohol (XV) and the base may be used in proportions of from 1 to 10 equivalents and 0.5 to 50 equivalents to one equivalent of the compound (1-5), respectively.

As a solvent, you can use the following materials: aliphatic hydrocarbons (e.g. hexane, heptane, naphtha), aromatic hydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diethyl simple ether, diisopropyl simple ether), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, dietilen glycol, glycerin), amines, acids (for example, N, N-dimethylformamide), sulfur compounds (e.g., dimethylsulfoxide, sulfolan) and water. These solvents can be used individually or in combination. Examples of bases are inorganic bases (for example, hydrate of sodium oxide, potassium hydroxide) and alkali metal alcoholate (e.g. sodium methylate, sodium ethylate).

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that was described in procedure (A) to obtain the target compound (1), i.e. the compound (1-2).

Procedure (D).

This reaction is in General carried out in a solvent at a temperature of from about 50 to 150aboutC for from 2 to 100 hours Gloriouse, pomeroyi or Jodorowsky agents may be used in proportions of from 1 to 10 equivalents to one equivalent of the compound (VII).

Examples of solvents are aliphatic hydrocarbons (e.g. hexane, heptane), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane) and ethers (e.g. diisopropyl simple ether, dioxane, tetrahydrofuran, dietilen glycol dimethyl simple ether). These solvents may be used individually or in combination. As glorieuses, brainwashes or jodorowski agent can be used N-chlorosuccinimide, N-bromosuccinimide and N-iodosuccinimide.

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that described in procedure (A) to obtain the target compound (1), namely the compound (1-3).

Procedure E.

Connection aminothiazoline (1) in which R2I (VIII) with glorieuses, brainwashin or Jodorowsky agent.

This reaction is in General carried out in a solvent at a temperature of from 50 to 150aboutC for from 2 to 100 hours Gloriouse, pomeroyi or oderwise agents may be used in proportions of from 1 to 10 equivalents to one equivalent of the compound (VIII).

Examples of solvent and glorieuses, brainwashes or oderwise agents are the same as those that were listed in the procedure (D).

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that was described in procedure (A) to obtain the target compound (1), namely the compound (1-3).

Examples of compounds of aminothiazoline (1), obtained using the procedure described above, are given in table. 1.

It should be noted that the compounds of aminothiazoline (1) include their stereoisomers, have a weed-killing activity.

Connection aminothiazoline (II) can be obtained by the interaction of aniline derivatives (IX) with isothiocyanates (X) to get the thiourea (XI), which is then converted into the compound (II) (scheme 1).

This reaction is in General carried out in a solvent in TX from 1 to 5 equivalents to one equivalent of the compound (IX).

The solvent can be used aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl simple ether, diisopropyl simple ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl simple ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), nitro compounds (for example, nitroethane, nitrobenzene), tertiary amines (e.g. N, N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. N, N-dimethylformamide) and sulfur compounds (e.g., dimethylsulfoxide, sulfolan). These solvents can be used individually or in combination.

As a catalyst, which can be used for the conversion of compound (XI) in the compound (II), should be mentioned as an example of the acid (for example, triperoxonane acid, sulfuric acid) and bases (e.g. sodium methylate).

After completion of the reaction, the reaction mixture can be subjected to subsequent standard is>In accordance with this procedure the compound (I-I) can be directly obtained without isolation of compound (II).

The compound (II) can be also obtained by the interaction of compounds aminothiazoline (III) with a base.

This reaction is in General carried out in a solvent at a temperature of from about 0 to 200aboutC for 1 to 20 hours, the Base can be used in proportions of from 1 to 50 equivalents to one equivalent of the compound (III).

The solvent may be mentioned as examples of aliphatic hydrocarbons (e.g. hexane, heptane, naphtha), aromatic hydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diethyl simple ether, diisopropyl simple ether, dioxane, tetrahydrofuran, dietilen glycol dimethyl simple ether), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol, glycerin), acid amides (for example, formamide, N, N-dimethylformamide, ndimethylacetamide) and sulfur compounds (e.g., dimethylsulfoxide, sulfolan). These solvents may be used individually or in combination. Examples of bases can be inorganic osnovnie sodium, t-butyl sodium).

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that was described in procedure (A) to obtain the target compound (II).

In accordance with this procedure, the compound (I-I) can also be obtained directly without isolation of compound (II).

The compound (VIII) can be obtained by the interaction of compounds aminothiazoline (1-3), in which R10is bromine, with a regenerating agent such as a hydride of anti -.

This reaction is in General carried out in a solvent at a temperature of from about 0 to 200aboutC for from 1 to 30 hours reducing agent can be used in proportions of from 1 to 100 equivalents to one equivalent of the compound (1-3) in which R10is bromine.

The solvent can be used aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diethyl simple ether, diisopropyl simple ether, dioxane, tetrahydrofuran, diethylene glycol, dimethyl simple ether), ketones (for example, tracecut, butyl acetate, diethylmalonate), nitro compounds (for example, nitroethane, nitrobenzene), NITRILES (e.g. acetonitrile, isobutyronitrile), acid amides (e.g. N, N-dimethylformamide) and sulfur compounds (e.g., dimethylsulfoxide, sulfolan). These solvents may be used individually or in combination.

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that was described in procedure (A).

Connection aminothiazoline (III) can be obtained according to the method described in the article in J. Am. Chem. Sos. 1079 (1984). Namely, the compound (III) can be obtained by the interaction of aniline compounds (XVI) with isothiocyanates (X) to obtain the compound of thiourea (XVII), which is then treated halogenation agent.

The connection of aminothiazoline (VII) can be obtained by the interaction of thiourea (XXVI) with a halide (XXVII) to get aminothiazoline (XXVIII), which is then treated with compound (V), (XIV) or (VI) under the same conditions that were described in procedure (B).

The connection of aminothiazoline (VII) can also be obtained by the interaction of thiourea (XXX) with the halide (XXVII).

aboutC for 1 to 100 hours Acid can be used in proportions of from 1 to 1000 equivalents per one equivalent of the compound (1-4).

Examples of the solvent are aromatic hydrocarbons (e.g. benzene, toluene, xylene), ethers (e.g. diethyl simple ether, diisopropyl simple ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl simple ether), fatty acids (e.g. formic acid, acetic acid, oleic acid), alcohols (e.g. methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, 2-methoxyethanol, diethylene glycol, glycerin and water. These solvents may be used individually or in combination. Examples of acids are sulfuric acid and hydrochloric acid, are preferred.

After completion of the reaction, the reaction mixture can be subjected to standard post-processing according to the same scheme that was described in procedure (A) to obtain the compound (IV).

Alternatively, after completion of the reaction, the reaction mixture can be concentrated under reduced pressure, to obtain a base compound (IV). Although the compound (IV) obtained by neutralizing onmary compounds (IV), obtained in accordance with the described procedure, are given in table. 2.

For practical use of the compounds of aminothiazoline (1), they in General are included in the composition with the known solid or liquid carriers or diluents as well as surface-active agents, or other auxiliary agents in order to obtain well-known forms such as emulsifiable concentrates, wettable powders, flowable compositions, granules and dispersible in water pellets.

These compositions contain compounds of aminothiazoline (1) as an active ingredient in a concentration in the range from about 0.02 to 90 wt. in a preferred embodiment, from about 0.05 to 80 wt.

Examples of the solid carriers or diluents are finely ground powders or granules of kaolin, attapulgite, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, powdered walnut shells, urea, ammonium sulfate and synthetic water silicon dioxide. As the liquid carrier or diluent can be used aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, 2-ethoxyethanol), ketones (e.g. acetone, collectinformation, acetonitrile and water.

Surface-active agent used for the preparation of emulsions, dispersions or suspensions, may be of any type, such as anionic or non-ionic. Examples of surface-active agents include alkyl sulphates, alkyl sulphonates, alkylarylsulphonates, diallylmalonate, phosphates polyoxyethyleneglycol ethers, polyoxyethylene alilovic ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, esters of fatty acids sorbitan and esters of fatty acids, polyoxyethylene sorbitol. Examples of the auxiliary agents include ligninsulfonate, alginate, polyvinyl alcohol, gum Arabic, CMC (carboxymethyl cellulose) and DADS (phosphate, isopropyl acid).

Connection aminothiazoline (1) in General include in any appropriate form and used for application prior to emergence or after emergence for weed control by tillage, foliage or irrigation water. This treatment involves applying to the surface of the soil before or after sowing, the incorporation into the soil before planting or transfer of seedlings, etc., the Processing of the leaves can be accomplished PR can also be applied directly to weeds, if you want to protect it from chemical attack foliage crops.

Doses of the compounds of aminothiazoline (I) may vary depending on prevailing weather conditions, used shape, season, method of application, soil type, crop species and weeds, etc. In General, however, doses are changed in the range from about 10 to 5000 g in a preferred embodiment, from about 20 to 2000 g of active ingredient per hectare. Herbicide composition, designed in the form of emulsifiable concentrate, wettable powder or fluid compositions can in General be used by diluting it with water to a volume of approximately 100 to 1000 l/ha, if necessary with the addition of auxiliary agents, such as enhancing the spreading agent. Herbicide composition, designed in the form of granules can in General be used as such without dilution.

Examples of reinforcing spreading agents include, along with surface-active agents, acid (ester) polyoxyethylene resin, ligninsulfonate, salt of abietic acid, dinaftiletilena and paraffin.

Connection Imin what's gardens, pastures, lawns, forests and non-agricultural fields. In addition, the compounds of aminothiazoline (1) can also be used together with other herbicides to improve weed-killing activity, and in some cases can be expected synergetic effects. In addition, these compounds can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, modifiers, soil, etc.

P R I m e R 1. Procedure A.

A mixture of acetyl chloride (2,75 g) and acetonitrile (70 ml) was cooled to 0aboutAnd to this mixture was added potassium thiocyanate (3.57 g), then it was stirred at room temperature for 6 hours After cooling to 0aboutIn the reaction mixture was added 3-trifluoromethyl-4-fluoro-N-propargylamine (7.6 g), and stirring was continued at room temperature for 3 hours

After removal of the solvent under reduced pressure, the concentrated residue was extracted with ethyl acetate (300 ml) and the extract was washed with water. After removal of the solvent was obtained crystals (8.5 g). These crystals were slowly added to sulfuric acid (25 ml) at a temperature of 0aboutC and stirring continued at 0aboutC for 0.5 is ovali aqueous solution of hydrate of sodium oxide, to obtain 8 g of 2-acetylamino-3-/3-trifluoromethyl-4-forfinal/-5-methylthieno - Lin (compound 1), melting point 179,0aboutC.

P R I m e p o l I h e n and I 2. Procedure ().

In the mixture of the hydrochloride of 2-imino-3-/3-trifluoromethyl-4 - forfinal/-5-methylthiazole (0,62 g) and triethylamine (0,61 g) in ethyl acetate (20 ml) at 0aboutWith the added anhydride triperoxonane acid (0,42 g). After stirring at room temperature for 3 h, the residue was extracted with ethyl acetate (100 ml) and the extract was washed with water. The solvent was removed under reduced pressure to obtain crystallization. These crystals were washed with hexane to obtain 0.45 g of 2-triptorelin-3-/3 - trifluoromethyl-4-forfinal/-5-methylthiazole (compound 2), the melting point 119,4aboutC.

Using the same procedure that was described above, the received connection aminothiazoline (1) listed in table. 3.

Compounds (1) and (7) received in accordance with the procedure of example 1 at the same time as the procedure in example 2 was used to obtain other compounds.

P R I m e p o l I h e I o n 3. (i) a Mixture of 2-acetylamino-3-/3 - trifluoromethyl-4-forfinal/-5-methylthiazole (3.5 g) and hydrochloric acid (36% 3.5 Melanie, and the residue was isolated and washed with a small amount of isopropanol and hexane, to obtain 2.8 g of 3-/3-trifluoromethyl-4-forfinal/-5-methyl-2 - aminothiazoline of hydrochloride (compound /i/).

(ii) In a mixture of ethyl acetate (50 ml) and aqueous potassium carbonate solution (20 ml) were added hydrochloride(3-/3-trifluoromethyl - 4-feranil)-5-methyl-2-aminothiazoline (1 g) and the mixture was stirred. The organic layer was isolated and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain 0.7 g of 3-/3-trifluoromethyl-4-forfinal/-5-methyl-2-imino-thiazoline in the form of butter.

Using the same procedure that was described above, the received connection aminothiazoline (IV) listed in table. 4.

Below are examples illustrating the practical embodiment of the herbicide composition according to the invention, in which parts are mass. The connection number of the active ingredient corresponds to the number of the table. 3.

Preparative form of example 1.

Fifty parts of any of the compounds NN 1-21, 23-25, 3 hours ligninsulfonate calcium, 2 hours lauryl sodium and 45 p.m. synthetic aqueous silica thoroughly stirred at z grinding to get the 1 to 25, 15 PM "Toxanone R L" (manufactured by industry surface-active agent, the company Sannio Kazei K. K. ) and 80 hours of cyclohexanone were thoroughly stirred to obtain an emulsifiable concentrate.

Preparative form of example 3.

Two parts of any of the compounds 1-21, 23-25, 1 h synthetic water silicon dioxide, 2 hours ligninsulfonate calcium, 30 hours of bentonite and 65 hours of kaolin are thoroughly mixed while grinding. The mixture was then stirred with water, granulated and dried to obtain granules.

Preparative form of example 4.

Twenty-five parts of any one of compounds 1-21, 23-25 mixed with 3 hours of monooleate polyoxyethylene sorbitol, 3 hours carboxymethyl cellulose (CMC) and 69 hours and water was spraying up until the particle size of the mixture becomes less than 5 microns to obtain a suspension.

Biological data connection aminothiazoline (1) as a herbicide are illustrated in the examples of tests that determined the phytotoxicity relative to agricultural crops and herbicide activity in relation to weed through visual observation of the degree of germination and growth inhibition, and these data activniy with untreated plants, and the index of "10" to the complete destruction or death of the test plants. The number of compounds in biological data corresponds to the number shown in the table. 3.

The compounds listed in table. 5, used for comparison.

P R I m e R and s p s t a n and th 1.

Cylindrical plastic roots (diameter 10 cm, height 10 cm) were filled with soil from the upper layers and planted the seeds of barnyard grass Japanese, ipomea high and limnocharis, and covered with soil. The specified quantity of the test compound was administered in the emulsifiable concentrate as in preparative form of example 2 and diluted with water and this mixture was sprayed on the soil surface using a small hand sprayer at a spray volume of material 1000 l/ha Subjects the plants were grown in a greenhouse for 20 days and studied herbicide activity. The results are presented in table. 6.

P R I m e R and s p s t a n and th 2.

Cylindrical plastic pots (diameter 10 cm, height 10 cm) were filled with top soil layers and planted the seeds of barnyard grass, ipomea, radish and limnocharis, then cultivated in a greenhouse for 10 days. The specified quantity of the test compound was administered in the form of emulsifiable concentrate, sbrasyvali over the foliage of the test plants by means of a small hand sprayer at a dose of 1000 l/ha The subjects of the plants grown in the greenhouse for 20 days and studied herbicide activity. The results are collected in table. 7.

P R I m e R and s p s t a n and th 3.

Cylindrical plastic pots (diameter 8 cm, height 12 cm) were filled with soil from the rice fields and planted the seeds batoshevo millet (Echinochloa oryzicola) and cane field (Scirpus juncoides) to a depth of 1-2 cm Soil watered with water to provide irrigation conditions, and seedlings of rice in stage 2 of the sheet transported in the soil, and subjects the plants were grown in the greenhouse. Six days later (by this time the seeds begin to germinate) a specified number of test compounds that are converted into finished form of emulsifiable concentrate as in example 2 preparative forms, and diluted with water (2.5 ml) was applied in relation to the pots with the plants by watering. Subjects plants were grown for 19 days in the greenhouse and tested herbicide activity and phytotoxicity. The results are shown in table. 8.

P R I m e R and s p s t a n and th 4.

Trays (33 cm x 23 cm x 11 cm) were filled with soil Nagorno-field and depth of 1-2 cm was sown seeds of cotton, ipomea, black nightshade, Alopecurus giant, barnyard grass and sorghum Aleppo. the ore 2 preparative forms it was diluted with water and the resulting mixture was sprayed on the soil surface using a small hand sprayer at a dose of 1000 l/ha Subjects the plants were grown in a greenhouse for 20 days and studied herbicide activity and phytotoxicity. The results are collected in table. 9.

P R I m e R and s p s t a n and th 5.

The Wagner pots (1/5000 Ara) were filled with soil of rice fields and seeds batoshevo millet (Echinochloa oryzicola) and broadleaf weeds (namely, full-color, rotary branched, pomoynitska, Ammannia multiflora) were planted at a depth of 1-2 cm Soil watered with water in order to create conditions of irrigation and rice seedlings at the stage 3 of the sheet to be lifted into her, and subjects the plants were grown in the greenhouse. Five days (by this time the seeds batoshevo millet begin emerging) after a specified number of the test compounds were introduced in the emulsifiable concentrate as in example 2 preparative forms and diluted with water mixture (10 ml) was applied to the pots by spraying. Subjects the plants were grown for 19 days in the greenhouse, with studied herbicide activity and phytotoxicity. The results are collected in table. 10. During processing, the depth of the water in the pots was kept at 4 cm and within posleduyu 6. Boxes (33 cm x 23 cm x 11 cm) were filled with top soil and seeds Veronica foreign and wheat were planted at a depth of 1-2 cm Specified number of the test compounds were included in the emulsifiable concentrate as in example 2 preparative forms was diluted with water and the resulting mixture was sprayed on the soil surface by means of an automatic sprayer at a dose of 1000 l/ha Subjects the plants were grown in the greenhouse for 25 days, and studied herbicide activity and phytotoxicity. The results are collected in table. 11.

1. Aminothiazoline formula I

< / BR>
where R1halogen or halo(lower) alkyl;

R2is lower alkyl or bromine;

R3- (lower alkyl) - carbonyl, (lower cycloalkyl)carbonyl, (lower alkoxy) - carbonyl or (lower alkyl)sulfonyl, all of which may be optionally substituted by at least one Deputy, selected from halogen, lower alkyl, lower alkoxy;

R4halogen.

2. Connection on p. 1, wherein R1- halogen, halo(C1- C3)alkyl;

R2is lower alkyl or bromine;

R3- C1- C6-alkylsulphonyl,3- C6-cycloalkylcarbonyl,1- C6-alkoxycarbonyl Deputy selected from halogen, C1- C3-alkyl, C1- C3-alkoxy;

R4halogen.

3. Connection on p. 2, wherein R4is paraprotein.

4. Connection on p. 3, wherein R4- fluoride.

5. Connection on p. 2, wherein R1- halo(C1- C3)-alkyl.

6. Connection on p. 5, wherein R1- trifluoromethyl.

7. Connection on p. 2, wherein R2- C1- C2-alkyl.

8. Connection on p. 2, wherein R3- C1- C6-alkylsulphonyl or3- C6-cycloalkylcarbonyl, and both can be optionally substituted by at least one Deputy, selected from halogen, C1- C3-alkyl and C1- C3-alkoxy.

9. Connection on p. 8, wherein R2- C1- C2-alkyl.

10. Connection on p. 9, wherein R4the fluorine in the para-position.

11. The method of producing aminothiazoline formula I

< / BR>
where R1- halogen, galonsky alkyl;

R3- (lower alkyl)carbonyl, (lower cycloalkyl)carbonyl, (lower alkoxy)celestiales, selected from halogen, lower alkyl, lower alkoxy;

R4- halogen; R6Is h or methyl,

characterized in that includes the interaction of the compounds of aminothiazoline formula II

< / BR>
where R1, R3, R6and R4have the specified values,

with a base or acid.

12. The method of producing aminothiazoline formula I

< / BR>
where R1- halogen, galonsky alkyl;

R3- (lower alkyl)carbonyl, (lower cycloalkyl)carbonyl, (lower alkoxy)carbonyl or (lower alkyl)sulfonyl, all of which may be optionally substituted by at least one Deputy, selected from halogen, lower alkyl and lower alkoxy;

R4- halogen;

R6Is h or methyl,

characterized in that includes the interaction of the compounds aminothiazoline formula IV

< / BR>
where R1, R4and R6have the specified values,

with the compound of the formula R3- Cl or R3-O-R3in the presence of base or with the compound of the formula R3-O-N, where R3has the specified values.

13. Aminothiazoline compound of formula IV

< / BR>
where R1- galonsky alkyl;

R4- halogen;

R6- vedeniya aminothiazoline the compounds of formula IV

< / BR>
where R1- halo (C1- C3)alkyl;

R4- halogen;

R6is hydrogen,

characterized in that it comprises the hydrolysis of the compounds of formula I

< / BR>
where R1, R4and R6have the specified values;

R7- C1- C6-alkylsulphonyl,

with acid.

16. Herbicide composition comprising the active ingredient and additives target, characterized in that it contains as active ingredient herbicide-effective amount of compound 1 on p. 1, where R1- halogen, galonsky alkyl;

R2is lower alkyl or bromine;

R3- (lower alkyl)carbonyl, (lower cycloalkyl)carbonyl, (lower alkoxy)carbonyl or (lower alkyl)-sulfonyl, all of which may be optionally substituted by at least one Deputy, selected from halogen, lower alkyl, lower alkoxy;

R4halogen.

17. The composition according to p. 16, wherein the effective amount is from 2 to 50% of the active ingredient.

18. Way to destroy unwanted weeds, including the introduction herbicide-effective amount of an active compound, characterized in that it is a connection 1 p. 1, where R
R4- halogen,

in areas where there are or will be growing unwanted weeds.

19. The method according to p. 18, wherein the effective amount is 16 - 2000 g/ha

 

Same patents:

The invention relates to the basic organic synthesis and concerns a method for obtaining asymmetrically disubstituted ureas of General formula I

R-NH--Nwhere R is phenyl, unsubstituted or mono - or multiply substituted by halogen atom, lower alkyl, lower alkoxygroup, arroceros, trifluoromethyl, and unsubstituted or once substituted lower alkoxygroup benzothiazolyl, or benzoxazolyl, R1and R2means a hydrogen atom or lower alkyl, and R1and R2cannot simultaneously denote a hydrogen atom

The invention relates to thiazole derivative, method for their production and their use as fungicides

The invention relates to new aminoven derivatives, processes for their production and insecticide containing as selective compounds listed derivatives

FIELD: organic chemistry, pesticides, agriculture.

SUBSTANCE: invention relates to compounds that elicit high pesticide activity and can be used in control of pests of domestic and agricultural animals. Indicated compounds show the formula (I):

wherein R1 means halogen atom, (C1-C6)-halogenalkyl; R2 means hydrogen atom (H), (C1-C6)-alkyl, (C1-C6)-alkylene-phenyl; X1 means nitrogen atom (N); X2 means group C(CN); X3 means oxygen atom (O); Q means CH; R3 and R4 mean independently of one another hydrogen atom (H) or in common with carbon atom with which they are bound form (C3-C7)-cycloalkyl ring; R5 means a substitute taken among group including (C1-C6)-halogenalkyl, halogen atom being if m above 1 then substitutes R5 can be similar or different; m = 1, 2 or 3; n = 0 or 1. Also, invention describes a method for their preparing and method for control of pests.

EFFECT: valuable pesticide properties of compounds.

7 cl, 3 tbl, 14 ex

FIELD: agriculture.

SUBSTANCE: invention relates to composition for seed pickling in form of water suspension concentrate containing thebuconazole and thiabendazole in ratio from 20:1 to 1:20 as active ingredients, nonionic and anionic surfactants, thickener, antifreeze, antifoaming agent, conserving agent, pigment, mineral or vegetable oil, lubricating agent, and water. Preparation of present invention has long shelf-life, freeze resistance, heat aging stability, beneficial effect on plant germination and harvest, and high biological activity. Method for controlling of plant diseases also is disclosed.

EFFECT: seed pickling composition of improved quality.

6 cl, 6 tbl, 5 ex

FIELD: agriculture, organic chemistry.

SUBSTANCE: invention relates to agent for controlling of plant pathogen fungi containing compound of general formula I as active ingredient, wherein X represents =N-; E represents NO2 or CN; R representsthiazolulmethyl or pyridylmethyl substituted with halogen; A represents hydrogen; Z represents C1-C4-alkylamino group; or A and Z together with atoms bonded thereon form thiazolidine, imidazolidine, hexahydro-1,3,5-triazine, N2- and N5-substituted with two C1-C4-alkyl in alkyl group, 6-membered saturated heterocycle fragment including additionally oxygen and N-(C1-C4)alkyl heterogroup; and fungicide compound selected from group containing cyproconazole, triadimenol, methalaxide, azoxistrobin, kresoximmethyl, etc., in weight ratio compound of formula I/fungicidal agent of 1:(0.1-10). Also disclosed is insecticide agent containing compound of formula I and compound selected from group containing cyproconazole, azoxistrobin, kresoximmethyl, biterthanol, tiram, methalaxide, etc. in ratio of 1:(0.1-10).

EFFECT: enhanced assortment of agents for controlling of plant pathogen fungi and agents for insect controlling.

4 cl, 15 tbl, 15 ex

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention relates to an insecticide-acaricide agent comprising a mixture of compound of the formula (I): wherein X means halogen atom, (C1-C4)-alkyl, (C1-C4)-alkoxyl; W, Y and Z mean independently of one another hydrogen atom (H), halogen atom, (C1-C4)-alkyl, (C1-C4)-alkoxyl; A means H, (C1-C6)-alkyl; B means H, methyl or ethyl; A and B in common with carbon atom to which they are bound form saturated unsubstituted (C3-C6)-ring or substituted with (C1-C4)-alkoxy-group; D means H, (C1-C6)-alkyl; G means H or one of the following groups: (b) or (c) wherein L means oxygen atom (O); M means O; R1 means (C1-C10)-alkyl, (C3-C6)-cycloalkyl that if necessary can comprise one nitrogen atom (N) or O; R2 means (C1-C10)-alkyl and agonist, respectively, antagonist of nicotine acetylcholine receptors chosen from the group comprising compounds of formulas: (IIa) (IIe) (IIg) (IIh) (IIi) (IIk) (IIl) and (IIm) taken in synergetically effective ratio.

EFFECT: valuable biological properties of substances.

6 cl, 22 tbl, 6 ex

FIELD: herbicides, agriculture.

SUBSTANCE: invention describes a herbicide agent with selective effect comprising a combination of biologically active substances and involving the following components: (a) compound of the formula (I) given in the invention description wherein Q1 means oxygen atom (O); Q2 means O; R1 means alkyl with number of carbon atoms from 1 to 6; R2 means alkyl with number of carbon atoms from 1 to 6; R3 means alkyl with number of carbon atoms from 1 to 6 substituted if necessary with (C1-C4)-alkoxyl or alkoxy-group with number of carbon atoms from 1 to 6; R4 means alkyl with number of carbon atoms from 1 to 6 or cycloalkyl with number of carbon atoms from 3 to 6, and salts of compounds of the formula (I) also, and (b) compound improving compatibility with crop plants and chosen from compounds of the following group: AD-67, cloquintocet-methyl, dichloramide, phenchlorazol-ethyl, flurazol, furylazol, isoxadiphen-ethyl, mefenpir-diethyl, MON-7400, compound of the formula (IId) given in the invention description, compound of the formula (IIe) given in the invention description wherein per 1 weight part of compound of the formula (I) or its salt is taken from 0.4 to 200 weight parts of compound of the group (b). Proposed herbicide agent prevents damage of crop plats and can be used for selective control against weeds in cultures of useful plants, for example, cereals and maize.

EFFECT: valuable properties of herbicide agent.

7 cl, 36 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to a malononitrile compound with formula (I): where one of X1, X2, X3 and X4 stands for CR100, where R100 is a group with formula (II) each three of the other X1, X2, X3 and X4 is nitrogen or CR5, under the condition that, from one to three of X1, X2, X3 and X4 stands for nitrogen, Z is oxygen, sulphur or NR6. The malononitrile compound can be used a pesticide in agriculture.

EFFECT: obtaining a new pest control compound and its use as an active ingredient of a pesticide composition.

18 cl, 180 ex

FIELD: chemistry.

SUBSTANCE: described are compounds of formula (I), in which Ar represents group of formula (A), (B1), (B2) or (C), or (D1), or (D2); R1, R2, R3, R4, R5, n, A1, A2, A3, A4, A5, Ka, Kb, L, M, V, W, X, Y, Z havevalues, determined in i.1 of invention formula, fungicide composition and method of combatting phytopathogenic fungi or their elimination, using compounds of formula (I).

EFFECT: high fungicide activity.

22 cl, 142 tbl, 34 ex

FIELD: agriculture.

SUBSTANCE: composition preventing plant diseases including components I and II as active ingredients is described. Component I is (RS)-N-[2-(1,3-dimethylbutyl)thiophene-3-yl]-1-methyl-3-trifluoromethyl-1H-pyrazol-4-carboxamides. Component II is selected from tetrakonazol, flutriafol, imibenkonazol, triadimefon, simekonazol, oxpokonazol fumarate, protiokonazol, bupirimate, spyroxamine, metiram, dodine, anilazine, chlozolinate, oxicarboxine, ethaboxam, iprovalikarb, pirazophos, phtorimide, diflumetorim, fenhexamide, famoxadone, fenamidone, ciazofamide, zoxamide, ciflufenamide, boskalid, isopropyl bentyavalikarb, pikoxistrobine, piraklostrobine, fluoxastrobine or dimoxistrobine. Also, the method preventing plant disease is described.

EFFECT: composition has synergistic effect which is not expected for each separate components, is able to significant increase of preventive effect against different phytopathogens with lower quantity of chemicals and do not invoke phytotoxic lesion.

2 cl, 9 tbl, 6 ex

FIELD: agriculture.

SUBSTANCE: substituted pyrazole-carbonic anilide derivatives of formula (I) are described, where R1 represents H, alkyl, alkyl carbonyl, alkenyl carbonyl, phenyl alkyl, phenyl carbonyl; R2 represents H, halogen, alkoxy; G represents alkyl, alkenyl; Z represents O; X represents H, halogen, alkyl; Y1 represents alkyl, alkenyl; Y2 represents halogen, C1-C6alkyl, m is equal to 1 or 2; and n is equal to 1, and their salts, acaricide for agriculture, such as pyrazole carbonic anilide derivatives of formula (I) and method for its application. Intermediate compound of formula (II) is also described, as well as 1.3-dimethyl-5-trifluoromethylpyrazole-4-carbonic acid.

EFFECT: improved use of new acaricides.

12 cl, 5 tbl, 20 ex

FIELD: medicine.

SUBSTANCE: there are described synergistic fungicidal combinations of biologically active substances which contain one carboxamide of general formula (I) , (group 1) where A, R1, R2 and R3 have values presented in the patent claim, and a biologically active substance chosen from compound groups specified in the patent claim (2) - (17) have. There is described application of said agent for undesired plant pathogenic fungi control.

EFFECT: extended range of the agents for undesired plant pathogenic fungi control.

8 cl, 13 tbl, 12 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to novel crystalline forms that can be used as components in preparing a solid pharmaceutical antidiabetic composition and antidiabetic medicinal agent. Invention relates to α-form of crystal and β-form of crystal of (R)-2-(2-aminothiazol-4-yl)-4'-{2-(2-hydroxy-2-phenylethyl)amino)]ethyl}acetanilide. α-Form of crystal shows the heat-absorption peak at 142-146°C in DSC-analysis and main peaks of X-rays powdery diffraction 5.32, 8.08, 15.28, 17.88, 19.04, 20.20, 23.16 and 24.34 in 2θ(°) units, it doesn't show hygroscopicity but possesses stability and therefore can be used as a medicinal agent. β-Form of crystal shows heat-absorbing peaks at 90-110°C and 142-146°C in DSC-analysis and main peaks in X-rays powdery diffraction 9.68, 19.76, 20.72, 22.10 and 23.52, it doesn't show hygroscopicity relatively and useful as an intermediate substance in preparing α-form of crystal also.

EFFECT: valuable properties of crystal.

8 cl, 2 tbl, 9 dwg, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 2-amino-5-methylthiazole used as an intermediate compound in synthesis of drugs. Method for synthesis of 2-amino-5-methylthiazole involves the following steps: chlorination reaction of propionic aldehyde with sulfuryl chloride, successive addition of lower alcohol and alkali aqueous solution to alkaline pH value of medium, separation of organic phase containing 2-chloropropionic aldehyde acetal, condensation of acetal with thiourea. Organic phase is added directly to thiourea in acid aqueous solution. Method provides increasing yield of the end product and to simplify the process.

EFFECT: improved method of synthesis.

1 cl, 3 ex

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