Phenyl-substituted heterocyclic 1,3-ketoenols, method for their preparing, herbicide agent based on thereof and method for control of weed growth

FIELD: organic chemistry, herbicides.

SUBSTANCE: invention describes phenyl-substituted heterocyclic 1,3-ketoenols of the formula (I): wherein R1 and R3 mean independently of one another ethyl or (C1-C2)-alkoxy-group; Q means the group of the formula (Q1): or (Q2): wherein R4 and R5 in common with atoms to which they are joined form 5-7-membered cycle that can comprise additionally anellated alkylene chain consisting of 2-6 carbon atoms that, in turn, can comprise two heteroatoms taken among oxygen atom, and indicated cycle can be substituted with halogen atom, hydroxy-group, (C1-C6)-alkoxy-group, (C1-C6)-alkoxy-(C1-C6)-alkoxy-group, (C1-C4)-alkylcarbonyloxy-group, hydroxy-(C1-C4)-alkoxy-group, hydroxycarbonyl-(C1-C2)-alkoxy-group, methoxycarbonyl-(C1-C2)-alkoxy-group, methoxyimino-, methoxyethoxyethoxy-group; R6 and R7 means (C1-C10)-alkyl; R8 means hydrogen atom; X means oxygen atom; R20 means (C1-C10)-alkyl, and also agronomically acceptable salts and isomers of these compounds. Also, invention describes a method for preparing compounds of the formula (I), herbicide agent and a method for control of weed growth based on compounds of the formula (I). Invention provides preparing compounds possessing the herbicide activity.

EFFECT: improved preparing method, valuable properties of compounds and agents.

5 cl, 28 tbl, 5 ex

 

The present invention relates to new, herbicide active, substituted phenyl group of the heterocycles, method of production thereof, to the means of containing these compounds and to their use for controlling weeds, especially in crops of useful plants, or for inhibiting the growth of plants.

3-hydroxy-4-aryl-5-oxadiazoline derivatives with herbicide activity are described, for example, in EP-A-0508126, WO 96/25395 and WO 96/21652.

According to the invention were obtained new, substituted phenyl group heterocycles with herbicide and suppressing plant growth properties.

The object of the present invention is accordingly the compounds of formula I

in which R1and R3independently from each other mean ethyl or1-C2alkoxygroup,

Q means a group

where R4and R5together with the atoms to which they are attached, form a 5-7 membered cycle which optionally contains anilinophenol consisting of 2-6 carbon atoms alkylenes chain, which in turn can contain two heteroatoms selected from oxygen, while this cycle may be substituted with halogen, hydroxy-group, C1-C6alkoxygroup, C1-C6alkoxy-C1-C6Alcock is the group, C1-C4alkylcarboxylic, hydroxy-C1-C4alkoxy, hydroxycarbonyl-C1-C2alkoxy, methoxyimino, methoxyethoxyethoxy,

R6, R7means C1-C10alkyl,

R8means hydrogen,

G1, G2independently of one another denote hydrogen, -C(X1)-R20where X1means oxygen, and

R20represents C1-C10alkyl,

and agronomically acceptable salts, isomers and enantiomers of these compounds.

The alkyl groups occurring in the definition of substituents, can be unbranched or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and the isomers of Penteli, exile, reptile, octile, lonely and decile. Alkoxyalkyl represents, for example, methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxide, n-butoxymethyl, isobutoxy-n-butyl, sec-butoxymethyl and tert-butoxy-isopropyl, preferably methoxymethyl and ethoxymethyl. Alkoxygroup, alkoxyalkyl group, are derived from the above alkyl residues. Alkoxygroup preferably have a chain length of from 1 to 6 carbon atoms. Alkoxygroup represents, for example, methoxy, ethoxy-, propoxy-, isopropoxy, h-butoxy, isobutoxy-, second -, butoxy - and tert-butox the group, and isomers pentyloxy, hexyloxy, preferably methoxy and ethoxypropan. Alkoxyalkyl means, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxyphenyl or isopropoxide. Alkylthiomethyl represents, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiouracil, n-propylthiouracil, isopropylaminomethyl, isopropylaminoethyl, butylthioethyl, butylthioethyl.

In the definitions of the substituents, the number of carbon atoms refers to the total number of carbon atoms in the alkyl groups, and groups derived, such as alkenylacyl. Thus, under the concept C2-C3alkoxyalkyl fall methoxymethyl, methoxyethyl and ethoxymethyl.

The compounds of formula I can, including, depending on the type of substituents, can exist as geometric and/or optical isomers and mixtures of isomers, as well as in the form of the tautomers and mixtures of tautomers. All such compounds of formula I are also included within the scope of the present invention. For example, the compounds of formula I in which Q represents the Q1and G1represents hydrogen, can exist in the following tautomeric equilibrium forms:

If G1and G2have a good in which Orada value and formed jointly by the substituents R4and R5the cycle of asymmetrically substituted, annylirovan, for example, the compound of formula I can exist in the form of the isomer of formula Id

In the scope of the present invention also includes salts which the compounds of formula I can form with amines, bases of alkaline and alkaline-earth metal or Quaternary ammonium bases. Suitable for this purpose soleobrazutaya agents are described, for example, in WO 98/41089.

Thus, the invention relates also to the salts which the compounds of formula I can form with amines, bases of alkaline and alkaline-earth metal or Quaternary ammonium bases. Among the hydroxides of the alkali and alkaline-earth metals as salt-forming agents noteworthy are the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially sodium or potassium.

As examples of amines suitable for the formation of ammonium salts include ammonia and primary, secondary and tertiary C1-C18the bonds alkylamines, C1-C4hydroxyethylamine and C2-C4alkoxyalkyl, for example methylamine, ethylamine, n-Propylamine, Isopropylamine, the four isomeric butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, noelani is, the decylamine, pentadecylic, hexadecylamine, heptadecyl, octadecylamine, methylethylamine, metrizability, methylhexanamine, methylenediamine, methylpentadiene, methyloctadecane, ethylbutylamine, ethylheptylamino, atractylis, vexillationes, getselection, dimethylamine, diethylamine, di-n-Propylamine, Diisopropylamine, di-n-butylamine, di-n-amylamine, vitaminen, digoxigenin, gigatronik, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropylamine, N-butylethylamine, allylamine, n-butenyl-2-amine, pentenyl-2-amine, 2,3-dimethylbutene-2-amine, dibutyl-2-amine, n-hexenyl-2-amine, Propylenediamine, trimethylamine, triethylamine, tri-n-Propylamine, triisopropanolamine, tri-n-butylamine, triisobutylene, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and amoxicillin, heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, Hinkley and asain, primary arylamine, such as anilines, methoxyaniline, ethoxyaniline, , m-, p-toluidine, phenylenediamine, benzidine, naphthylamines and o-, m-, p-chloraniline, but primarily triethylamine, Isopropylamine and Diisopropylamine.

Preferred Quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(RaRbRcRd)]OH, the cat is Roy R a, Rb, Reand Rdindependently of one another denote C1-C4alkyl. Other suitable tetraalkylammonium base with other anions can be obtained, for example, by using anion-exchange reactions.

Other preferred compounds of formula I are distinguished by the fact that R4and R5together with the atoms to which they are attached, form a 5-7 membered cycle.

The compounds of formula I can be obtained by the coupling of compounds of formula XXX

in which Q represents the Q1, Q2while their deputies, except for the G1, G2have the above values, a G1, G2mean hydrogen, with a compound of formula XXXI

in which R1and R3are indicated for the formula I values, a Hal represents a chlorine, bromine or iodine, in the presence of an inert solvent, a base and a palladium catalyst at a temperature in the range from 30 to 250°C. the Reaction is preferably carried out in an atmosphere of inert gas.

Unexpectedly, it was found that the most preferred is getting above described compounds of formula I in which R1and R3means ethyl. Used to obtain these compounds of formula I, intermediates of formula XXXI, where R1 and R3means ethyl, and Hal represents a chlorine, bromine or iodine (formula XXXIa), are new compounds which have been specially developed for the implementation of this method and thus also constitute one of the objects of the present invention.

The compounds of formula XXX are known or can be obtained by known methods as described, for example, J.Chem. Soc. Perkin Trans. 1, (4), 877-884 (1987). The compounds of formula XXXI can be obtained, for example, by known methods, in particular by the reaction of Sandmeyer, from the corresponding anilines of formula XXXII

in which R1and R3are indicated for the formula I values, via diazonium salts. Such reactions are described, for example, in Vogel''s Textbook of Practical Organic Chemistry, 5th ed., B.S.Furniss, A.J.Hannaford, P.W.G.Smith, A.R.Tatchell; Longman Scientific & Technical 1989, str. The compounds of formula XXXII are known, some of them are commercially available or can be obtained analogously to known compounds.

Suitable for this reaction are such grounds as three(alkali metal)phosphate, hydrides of alkali and alkaline earth metal amides alkali and alkaline-earth metals and alkali metal alcoholate, such as tribalistic, sodium hydride, diisopropylamide lithium (DAL), Na-tert-butyl or tert-butlt. The most preferred Na-tert-butyl, tert-Buti is al, and tribalistic.

Suitable solvents are, for example, aromatic hydrocarbons such as xylene or toluene, ethers such as tetrahydrofuran, dioxane or etilenglikolevye ether, dimethylsulfoxide or tertiary amides, such as dimethylformamide, N-methylpyrrolidone or dimethylacetamide, or acyclic urea such as N,N'-dimethylpropyleneurea.

Suitable for accompanied by the formation of carbon-carbon links of combination reaction of compounds of formula XXX with a compound of formula XXXI palladievye catalysts are mainly complex compounds of palladium(II) or palladium(0), such as dihalogenide palladium(II)acetate, palladium(II)sulfate, palladium(II)dichloride bis(triphenylphosphine)palladium(II) (Pd(TTF)2Cl2), dichloride, bis(tricyclohexylphosphine)palladium(II)dichloride bis(tricyclohexylphosphine)palladium(II), bis(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphosphine)palladium(0). The palladium catalyst can also be obtained in situ from compounds of palladium(II) or palladium(0) as a result of complexing with the desired ligand, for which, for example, exposed complexing salt is palladium(II), for example dichloride palladium(II) (PdCl2) or palladium(II) acetate (Pd(OAc)2), combine with the desired ligand, for example triphenylphosphine (Ph 3), tricyclohexylphosphine or tricyclohexylphosphine, and with, respectively, the selected solvent, the compound of formula XXXI, compound of formula XXX and base. You can also use a bidentate ligand such as 1,1'-bis(diphenylphosphino)ferrocene or 1,2-bis(diphenylphosphino)ethane. In this case, subsequent heating of the reaction medium leads to the formation of in situ complex compounds of palladium(II), respectively palladium(0), required for accompanied by the formation of carbon-carbon links of combination reaction and then initiating the reaction. Palladium catalysts are used in quantities of from 0.001 to 50 mol.%; preferably from 0.1 to 15 mol.% in terms of the compound of formula XXXI.

The reaction temperature is selected depending on the solvent used and under certain conditions of pressure. It is preferable to conduct the reaction at atmospheric pressure.

The compounds of formula I in which Q represents the Q1you can get similar to the method described in WO 96/21652. The compounds of formula I in which Q represents O2can be obtained for example by the method described in EP-A-0415185, EP-A-0521334, EP-A-0355599 and EP-A-0442077. The compounds of formula I in which Q represents the Q3, Q4, Q6and Q7can be obtained by the method described, for example, in WO 96/35644 and WO 97/02243. Conn is of formula I, in which Q represents the Q5can be obtained, for example, similarly to the method described in WO 97/14667. Similar methods of preparing compounds of the formula I in which Q represents the Q7described in WO 97/16436. The compounds of formula I in which Q represents the Q8you can get similar patent US 5994274. The compounds of formula I in which Q represents the Q9you can get similar application JP 11-152273 And priority (from 19.11.1997, JP 318614), and the compounds of formula I in which Q represents the Q10, can be obtained according to J. Org. Chem. 44(26): 4906-4912 (1979) or J. Org. Chem. 42(7): 1163-1169 (1977) or similar methods.

Chemical transformations in the compounds of formula I is preferably carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, carbon tetrachloride or chlorobenzene, ethers, such as diethyl ether, etilenglikolevye ether, diethylethylenediamine ether, tetrahydrofuran or dioxane, NITRILES, such as acetonitrile or propionitrile, amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperature is preferably from -20 to +120°C. Such chemical transformations is usually is raised slightly exothermic, and they are usually performed at room temperature. To reduce the duration of the reaction or for initiating a chemical transformation of the reaction mixture can optionally be heated within a short time interval before the boiling point. To shorten the reaction can also add a few drops of a base as catalyst of the reaction. The reason is primarily suitable tertiary amines such as trimethylamine, triethylamine, Hinkley, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. For the same purpose as the bases can also be used inorganic bases such as hydrides, e.g. sodium hydride or calcium hydroxides, for example sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate or potassium, or hydrogen carbonates, such as potassium bicarbonate or sodium. The compounds of formula I can be distinguished in the usual way by concentration and/or evaporation of the solvent and purify by recrystallization or trituration of the solid residue in solvents in which they practically insoluble or laboratorii, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

For the envisaged according to the invention use compounds fo the mules I or the containing means can be used with all conventional agriculture processing methods, such as predsjedava processing, post-harvest processing and seed treatment, as well as various other methods and technologies, such as controlled release of the active substance. With this purpose the active substance from solution onto mineral granular media or polymer granules (urea/formaldehyde) and dried. Then if necessary, you can apply an extra coating the granulate in the shell), which allows for a certain amount of time to release the active substance in dosed quantities.

The compounds of formula I can be used as herbicides in an unmodified form, i.e. as they are the result of synthesis. More preferably, however, process them according to conventional methods with auxiliary substances commonly used in cooking techniques preparative forms of receiving, for example, mulgirigala concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, Farrukh Dustov, granules or microcapsules. Such formulation are described, for example, in WO 97/34485 on page 9-13. Processing methods, such as spraying, treatment in the form of mists (atomized spraying, dusting, treatment, and rasp syvania or watering, as well as the type of drug chosen in accordance with the objectives and the prevailing circumstances.

Preparative form, i.e. the compositions, compounds or mixtures containing the active substance of the formula I or at least one of the active substances of the formula I and usually one or more solid or liquid auxiliary substances (adjuvants)used in the preparation technology preparative forms, get a known method, for example by homogeneous mixing and/or grinding the active substances with adjuvants, for example solvents or solid carriers. In addition, when receiving preparative forms optionally, you can use surface-active substances (surfactants). Examples of solvents and solid carriers are described in particular in WO 97/34485 on page 6.

As surface-active substances depending on what should be included in formulations of the active substance of the formula I use nonionic, cationogenic and/or anionic surfactants and mixtures of surfactants with high emulsifying, dispersing and wetting properties. Examples suitable for this purpose anionic, nonionic and cationogenic surfactants are described in particular in WO 97/34485 on page 7 and 8. In addition, to obtain the proposed invention herbicide suitable means commonly used in the technology of the sentence is the service preparative forms surfactants, which are described in particular in "Me Cutcheon''s Detergents and Emulsifiers Annual", published by MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", publishing house Carl Hanser Verlag, München/Vienna, 1981 and M. and J. Ash, "Encyclopedia ofSurfactants", T.I-III, published by Chemical Publishing Co., New York, 1980-81.

The effectiveness of the proposed invention herbicide and inhibit the growth of plants containing herbicide effective amount of the compounds of formula I, can be improved through the use of adjuvants that are added to the tank with the preparation for spraying. Such adjuvants may constitute, for example, nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationogenic surfactants, silicone surfactants, derivatives, mineral oils, surfactants, derivatives of vegetable oils with or without added surfactants, alkylated derivatives of oils of vegetable or mineral origin with surfactants and without them, fish oil and other animal oils, as well as their alkyl derivatives with surfactants and without them, naturally occurring higher fatty acid, preferably 8-28 carbon atoms, and derivatives thereof in the form of alilovic esters, organic acids containing aromatic cyclic system and one or more esters of carboxylic acids and their alkyl derivatives and, in addition, suspensions of polymers of vinyl acetate or copolymers vinylic the Tata and esters of acrylic acid. A mixture of individual adjuvants among themselves, as well as their use in combination with organic solvents can further increase efficiency.

As an example, nonionic surfactants can be called polyglycolether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and ALKYLPHENOLS, which can contain preferably from 3 to 30 glycolether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and from 6 to 18 carbon atoms in the alkyl fragment of ALKYLPHENOLS.

Other suitable nonionic surfactants are water-soluble, preferably containing from 20 to 250 etilenglikolevykh groups and from 10 to 100 propylenglykolether groups, the addition products of polyethylene oxide to polypropylenglycol, ethylenediaminetriacetic and alkylpolyethylenglycol preferably 1-10 carbon atoms in the alkyl chain. These compounds typically contain from 1 to 5 etilenglikolevykh links on one propilenglikole link.

As other examples of nonionic surfactants should mention also nonylphenolethoxylates, polyglycidyl ether of castor oil, adducts of polypropylene-polyethylene oxide, tributyltinoxide, polyethylene glycol and octylphenoxypolyethoxyethanol.

In addition is also possible to use esters of fatty acids and polyoxyethylenesorbitan, such as polyoxyethylenesorbitan.

Among the anionic surfactants are preferred primarily alkyl sulphates, alkyl sulphonates, alkylarylsulphonates, alkylated phosphoric acid, and their ethoxylated derivatives. Alkyl residues typically contain from 8 to 24 carbon atoms.

Preferred nonionic surfactants are known under the following trade names: polyoxyethylene-cocoalkylamine (for example, AMIET®105 (firm Kao Co.)), polyoxyethylene-oleylamine (for example, AMIET®415 (firm Kao Co.)), nonylphenolethoxylates, polyoxyethylene-stearylamine (for example, AMIET®320 (firm Kao Co.)), N-polyethoxyethanol (for example, GENAMIN®(the firm Hoechst AG)), N,N,N',N'-Tetra(politicsimprovement)ethylendiamine (for example, TERRONIL®and TETRONIC®(BASF Wyandotte Corp.)), BRIJ®(firm Atlas Chemicals), ETHYLAN®CD and ETHYLAN®D (company Diamond Shamrock), GENAPOL®C, GENAPOL®O, GENAPOL®S and GENAPOL®X080 (firm Hoechst AG), EMULGEN®104P, EMULGEN®109P and EMULGEN®408 (firm Kao Co.), DISTY®125 (firm Geronazzo), SOPROPHOR®CY18 (firm Rhône Poulenc S.A.), NONISOL®(the company Ciba-Geigy), MRYJ®(the company ICI), TWEEN®(the company ICI), EMULSOGEN®(the firm Hoechst AG), AMIDOX®(firm Stephan Chemical Co.), ETHOMID®(firm Armak Co.), PLURONC ®(BASF Wyandotte Corp.), SOPROPHOR®461P (firm Rhone Poulenc S.A.), SOPROPHOR®496/P (firm Rhône Poulenc S.A.), ANTAROX FM-63 (firm Rhône Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (firm Osi Specialities).

If cationogenic surfactants it is first and foremost about the salts of Quaternary ammonium bases, which as N-substituents contain at least one alkyl residue with 8-22 C-atoms and the other substituents are lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues. As such salts are the preferred halides, methylsulfate or ethylsulfate, such as steartrimonium or benilde(2-chloroethyl)ethylammonium.

The oils used are either mineral or natural. Natural oils can also be of animal or vegetable origin. As animal oils are used mainly derived beef fat (tall oil)and fish oil (for example fat sardines) and their derivatives. Vegetable oils are typically oil from seeds of different origin. As an example, the most commonly used vegetable oils can be called coconut, rapeseed or sunflower oil and their derivatives.

The content of oil additives proposed in izobreteny the tool is usually from 0.01 to 2% in terms of working solution. Oil additive can, for example, be added in the desired concentration in the tank with the preparation for spraying after preparation of the working solution.

Preferred oil additives to offer in the invention means are oil of vegetable origin, for example rapeseed oil or sunflower oil, alkalemia esters of oils of vegetable origin, such as methyl derivatives, or mineral oil.

The most preferred oil additives contain alkalemia esters of higher fatty acids (C8-C22), especially methyl derivatives of C12-C18fatty acids, such as methyl ester of lauric acid, palmitic acid and oleic acid. Such esters are known as meilleur (CAS 111-82-0), metralleta (CAS 112-39-0) and methyl oleate (CAS 112-62-9).

The efficiency of oil additives can be improved by using them in combination with surfactants, such as nonionic, anionic or cationogenic surfactant. Examples suitable for this purpose anionic, nonionic and cationogenic surfactants are described in WO 97/34485 on page 7 and 8.

Preferred surfactants are anionic surfactants of the type dodecylbenzensulfonate, primarily their calcium salts, and nonionic surfactants of the type of ethoxylates of fatty alcohols. is the most preferred ethoxylated C 12-C22fatty alcohols with a degree of amoxilonline from 5 to 40. Examples of commercially available preferred surfactants are the products of type Genapol (company Clariant AG, Muttenz, Switzerland). The concentration of surfactants in terms of the total amount of additive is usually from 1 to 30 wt.%.

Examples of oil additives consisting of mixtures of oils, respectively, mineral oils or derivatives thereof with surfactants are products Edenor ME SU®, Emery 2231®(firm Henkel Tochtergesellschaft Cognis GMBH, Germany), Turbocharge®(firm Zeneca Agro, young Stoney Creek, Ontario, Canada) or most preferably Actipron®(company BP Oil UK Limited, UK).

In addition, to improve the efficiency of the mixture of the oil with surfactant additives allows adding thereto an organic solvent.

Suitable for this purpose solvents are, for example, Solvesso®(company ESSO) or Aromatic Solvent®(company Exxon Corporation).

The concentration of these solvents may be from 10 to 80 wt.% of the total mass.

Such oil supplements, which are described, for example, in US 4834908, most preferred for use in the composition proposed in the invention of money. The most preferred oil additive known under the name MERGE®produced by BASF Corporation and, in General, describe what and, for example, in US 4834908, column 5, as an example, SOS-1. Another preferred according to the invention with an oil additive is the product SCORE®(Novartis Crop Protection Canada).

Usually used in cooking techniques preparative forms and adjuvants of surfactants, oils, especially vegetable oils, their derivatives such as alkylated fatty acids and their mixtures, for example, preferably anionic surfactants, such as alkylated phosphoric acids, alkyl sulphates and alkylarylsulfonate, as well as higher fatty acids, which can also be used in the proposed invention the means and prepared from them in tanks solutions for spraying, described in particular in "Mc Cutcheon''s Detergents and Emulsifiers Annual", published by MC Publishing Corp., Ridgewood New Jersey, 1998, H. Stache, "Tensid-Taschenbuch", publishing house Carl Hanser Verlag, München/Wien, 1990, M. and J. Ash, "Encyclopedia of Surfactants", T.I-IV, published by Chemical Publishing Co., New York, 1981-89, G. Kapusta, "A Compendium of Herbicide Adjuvants", Southern Illinois Univ., 1998, L. Thomson Harvey, "A Guide to Agricultural Spray Adjuvants Used in the United States"published by Thomson Pubns., 1992.

Usually herbicide compositions contain from 0.1 to 99 wt.%, especially from 0.1 to 95 wt.% herbicide, from 1 to 99.9 wt.%, first of all, from 5 to 99.8 wt.% solid or liquid excipients to be included in the composition, and from 0 to 25 wt.%, first of all, from 0.1 to 25 wt.% Surfactants. If included in the sale of products before occhialini compounds or compositions in the form of concentrates, the end user typically uses diluted preparations. These preparations may also contain other additives, such as stabilizers, for example optional epoxydecane vegetable oil (epoxydecane coconut oil, rapeseed oil or soybean oil), antispyware, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, as well as fertilizers or other active ingredients.

Usually the consumption rate of the active substance of the formula I in the processing plant or its habitat ranges from 0.001 to 4 kg/ha, especially 0.005 to 2 kg/ha Required to achieve the desired action, the dosage can be determined empirically. This dose depends on the type of action, the stage of development of plants and weeds, and the treatment conditions (place, time, method) and taking into account these parameters may vary within wide limits.

The compounds of formula I possess herbicide and suppressing plant growth properties, allowing their use in crops of useful plants, especially in crops of cereals, cotton, soybeans, sugar beet, sugar cane cultivated on plantations crops, canola, corn and rice, as well as for non-selective weed control. Under cultivated plants should understand as well as plants, to which were the result of conventional methods of breeding or genetic engineering was developed tolerance to herbicides, accordingly to different classes of herbicides. Such crops include maize varieties IMI, corn varieties Poast Protected (tolerance sethoxydim), corn varieties Liberty Link corn varieties B.t./Liberty Link corn varieties IMI/Liberty Link corn varieties IMI/Liberty Link/B.t., corn varieties Roundup Ready corn varieties Roundup Ready/B.t.

Weeds, which according to the invention are fighting, can be both single-and dicotyledonous weed plants such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

With the invention it has been unexpectedly found that for use in the mixture with the proposed invention herbicide by means of suitable special antidotes known from US 5041157, US 5541148, US 5006656, EP-A-0094349, EP-A-0551650, EP-A-0268554, EP-A-0375061, EP-A-0174562, EP-A-0492366, WO 91/7874, WO 94/987, DE-A-19612943, WO 96/29870, WO 98/13361, WO 98/39297, WO 98/27049, EP-A-0716073, EP-A-0613618, US 5597776, EP-A-0430004, DE-A-4331448, WO 99/16744, WO 00/30447 and WO 00/00020. Therefore, the present invention relates also to the means of selective herbicide steps to fight with the grasses and weeds in crops of useful plants, especially in crops of corn and grain, which contains a herbicide of formula I and the antidote and protecting useful plants, but not the weeds, from phyto-toxic action of the herbicide, as well as to the use of such funds for combating weeds in crops of useful plants.

According to the invention it is, therefore, offers a means of selective herbicide action, which differs in its composition along with conventional inert excipients used in compositions, such as carriers, solvents and wetting agents, as active substance is a mixture of

a) herbicide effective amount of the compounds of formula I

in which R1, RCand Q have the above meanings, and

b) herbicide-antagonistically effective amount of any of compounds of formula X

in which R37means hydrogen, C1-C8alkyl or substituted C1-C6alkoxygroup or C3-C6alkenylacyl C1-C8alkyl, and X7means hydrogen or chlorine,

or the compounds of formula XI

in which E denotes nitrogen or Metin, R38means-CCl3, phenyl or substituted by halogen phenyl, R39and R40independently of one another denote hydrogen or halogen, a R41means C1-C4alkyl,

or the compounds of formula XII

in which R44and R45independently of one another denote hydrogen or halogen, and R46 , R47and R48independently of one another denote C1-C4alkyl,

or the compounds of formula XIII

in which And2represents a group

R51and R52independently of one another denote hydrogen, C1-C8alkyl, C3-C8cycloalkyl, C3-C6alkenyl, C3-C6quinil, groupor substituted C1-C4alkoxygroup or group

C1-C4alkyl or

R51and R52together form a C4-C6Allenby bridge which may be interrupted by oxygen, sulfur, SO, SO2, NH or-N(C1-C4by alkyl)-,

R53means hydrogen or C1-C4alkyl,

R49means hydrogen, halogen, cyano, trifluoromethyl, nitro-group, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRmor-OSO2-C1-C4alkyl,

Rgmeans hydrogen, halogen, a cyano, a nitro-group, C1-C4alkyl, C1-C4haloalkyl, C1-C4allylthiourea, C1-C 4alkylsulfonyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm, -OSO2-C1-C4alkyl, C1-C6alkoxygroup or C1-C6alkoxygroup, substituted C1-C4alkoxygroup or halogen, C3-C6alkenylacyl or C3-C6alkenylacyl, substituted with halogen, or C3-C6alkyloxy, or

R49and R50together form a C3-C4Allenby bridge which may be substituted with halogen or C1-C4the alkyl or form C3-C4alkenylamine bridge which may be substituted with halogen or C1-C4the alkyl or form together With4akadeemiline bridge which may be substituted with halogen or C1-C4the alkyl,

R50and Rhindependently of one another denote hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C6alkoxygroup, C1-C6allylthiourea or-COORj,

Rcmeans hydrogen, halogen, a nitro-group, C1-C4alkyl or a methoxy group,

Rdmeans hydrogen, halogen, a nitro-group, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4Ala is sulfonyl, -COORjor CONRkRm,

Remeans hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy group, or

Rdand Retogether form a C3-C4Allenby bridge,

Rp means hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy group,

Rq denotes hydrogen, halogen, a nitro-group, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4alkylsulfonyl, -COORjor CONRkRmor

Rp and Rq together form a C3-C4Allenby bridge,

Rr denotes hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy group,

Rs means hydrogen, halogen, a nitro-group, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4alkylsulfonyl, -COORjor CONRkRmor

Rr and Rs together form a C3-C4Allenby bridge,

Rt is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy group,

EN means hydrogen, halogen, a nitro-group, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alcalali the Nile, C1-C4alkylsulfonyl, -COORjor CONRkRmor

Rv and Ru together form a C3-C4Allenby bridge,

Rf and Rv denote hydrogen, halogen or C1-C4alkyl,

Rxand Ryindependently of one another denote hydrogen, halogen, C1-C4alkyl, C1-C4alkoxygroup, C1-C4allylthiourea, -COOR54, trifluoromethyl, nitro-group or a cyano,

Rj, Rkand Rmindependently of one another denote hydrogen or C1-C4alkyl or

Rkand Rmtogether form a C4-C6Allenby bridge which may be interrupted by oxygen, NH or-N(C1-C4by alkyl)-,

Rnmeans C1-C4alkyl, phenyl or substituted by halogen, C1-C4the alkyl, methoxy group, a nitro-group or a trifluoromethyl phenyl,

R54means hydrogen, C1-C10alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di (C1-C4alkylamino-C1-C4alkyl, halogen-(C1-C8alkyl, C2-C8alkenyl, halogen-C2-C8alkenyl, C3-C8quinil, C3-C7cycloalkyl, halogen-C3-C7cycloalkyl, C1-C8alkylsulphonyl, arylcarbamoyl, C3-C7cloudkicker, benzoyl which is unsubstituted or contains a phenyl ring with up to three identical or different substituents which are halogen, C1-C4alkyl, halogen-(C1-C4alkyl, halogen-(C1-C4alkoxygroup or C1-C4alkoxygroup, or means furoyl, thienyl, C1-C4alkyl, substituted phenyl, halogenfree, C1-C4alkylphenyl, C1-C4the alkoxyphenyl, halogen-C1-C4alkylphenyl, halogen-C1-C4the alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8alkoxycarbonyl, C3-C8alkanolammonium, C3-C8alkyloxyaryl, C1-C8alkylthiomethyl, C3-C8alkenylsilanes, C3-C8alkylthiomethyl, carbamoyl, mono-C1-C4alkylaminocarbonyl, di-C1-C4alkylaminocarbonyl, phenylenecarbonyl, which is unsubstituted or contains phenyl up to three identical or different substituents which are halogen, C1-C4alkyl, halogen-(C1-C4alkyl, halogen-(C1-C4alkoxygroup or C1-C4alkoxygroup, or one Deputy who is cyano or nitro-group, dioxolane-2-yl, which is unsubstituted or substituted by one or two C -C4alkyl residues, dioxane-2-yl, which is unsubstituted or substituted by one or two C1-C4alkyl residues, or C1-C4alkyl, which is substituted by a cyano, a nitro-group, carboxyla or C1-C8alkylthio-C1-C8alkoxycarbonyl,

or the compounds of formula XIV

in which R56and R57independently of one another denote C1-C6alkyl or C2-C6alkenyl or

R56and R57together form the group

where R58and R59independently of one another denote hydrogen or C1-C6alkyl, or

R56and R57together form the group

where R60and R61independently of one another denote C1-C4alkyl or

R60and R61together form a group -(CH2)5-,

R62means hydrogen, C1-C4alkyl or the groupor

R56and R57together form the groupor

where R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73, R74, R75, R76, R77and R78independently of the other denote hydrogen or C 1-C4alkyl,

or the compounds of formula XV

in which R80means hydrogen or chlorine, a R79means cyano or trifluoromethyl,

or the compounds of formula XVI

in which R81means hydrogen or methyl,

or the compounds of formula XVII

in which R82means hydrogen, C1-C4alkyl or C1-C4alkyl, substituted C1-C4alkyl-X2or C1-C4haloalkyl-X2-, or C1-C4haloalkyl, a nitrogroup, cyano, -COOR85, -NR86R87, -SO2NR88R89or-CONR90R91,

R83means hydrogen, halogen, C1-C4alkyl, trifluoromethyl, C1-C4alkoxygroup or C1-C4haloalkoxy,

R84means hydrogen, halogen or C1-C4alkyl, U, V, W1and Z4independently of one another denote oxygen, sulfur, C(R92R93, carbonyl, NR94groupor

thus R102represents a C2-C4alkenyl or C2-C4quinil, provided that

a) at least one of the ring members U, V, W1or Z4presented yet a carbonyl, and related respectively with these ring members of the ring member is a groupormoreover, such a group is present only once, and

b) two adjacent annular member of U and V, V and W1and W1and Z4cannot mean oxygen

R95and R96independently of one another denote hydrogen or C1-C8alkyl or

R95and R96together form a C2-C6alkylenes group,

A1means R99-Y1- or-NR97R98,

X2means oxygen or-S(O)s,

Y1means oxygen or sulphur,

R99means hydrogen, C1-C8alkyl, C1-C8haloalkyl, C1-C4alkoxy-C1-C8alkyl, C3-C6alkenylacyl-C1-C8alkyl or phenyl-C1-C8alkyl, with the phenyl ring may be substituted with halogen, C1-C4the alkyl, trifluoromethyl, methoxy group or a methyl group-S(O)s-C3-C6alkenyl, C3-C6haloalkyl, phenyl-C3-C6alkenyl, C3-C6quinil, phenyl-C3-C6quinil, oxetanyl, furyl or tetrahydrofuryl,

R85means hydrogen or C1-C4alkyl,

R86means in dorog, C1-C4alkyl or C1-C4alkylsulphonyl,

R87means hydrogen or C1-C4alkyl or

R86and R87together form a C4- or5alkylenes group,

R88, R89, R90and R91independently of one another denote hydrogen or C1-C4alkyl or

R88together with R89or R90together with R91independently from each other mean With4- or5alkylene, where one carbon atom may be replaced by oxygen or sulfur or one or two carbon atoms may be replaced by-NR100-,

R92, R100and R93independently of one another denote hydrogen or C1-C8alkyl or

R92and R93together represent a C2-C6alkylen,

R94means hydrogen or C1-C8alkyl,

R97means hydrogen, C1-C8alkyl, phenyl or phenyl-C1-C8alkyl, with the phenyl ring may be substituted by fluorine, chlorine, bromine, nitro-group, cyano, -co3C1-C4the alkyl or CH3SO2-C1-C4alkoxy-C1-C8alkyl, C3-C6alkenyl or C3-C6quinil,

R98means hydrogen, C1-C8alkyl, C3-C6alkenyl or C3-C6and kinil or

R97and R98together mean With4- or5alkylene, where one carbon atom may be replaced by oxygen or sulfur or one or two carbon atoms may be replaced by-NR101-,

R101means hydrogen or C1-C4alkyl,

r is 0 or 1, and

s denotes 0, 1 or 2,

or the compounds of formula XVIII

in which R103means hydrogen, C1-C6alkyl, C3-C6cycloalkyl, C3-C6alkenyl or C3-C6quinil, a R104, R105and R106independently of one another denote hydrogen, C1-C6alkyl, C3-C6cycloalkyl or C1-C6alkoxygroup, provided that one of substituents R104, R105and R106is other than hydrogen the value of the compounds of formula XIX

in which Z5means N or CH, n in the case when Z5represents N means 0, 1, 2 or 3, and when Z5represents CH, means 0, 1, 2, 3 or 4, R107means halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4haloalkoxy, a nitrogroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4alkoxycarbonyl is l, phenyl or fenoxaprop or substituted C1-C3the alkyl, C1-C3haloalkyl, C1-C3alkoxygroup, C1-C3haloalkoxy, halogen, cyano or nitro-group is phenyl or fenoxaprop, R108means hydrogen or C1-C4alkyl, R109means hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, C2-C6quinil, C1-C4haloalkyl, C2-C6haloalkyl, C2-C6haloalkyl, C1-C4alkylthio-C1-C4alkyl, C1-C4alkylsulfonyl-C1-C4alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkenylacyl-C1-C4alkyl or C1-C4alkyloxy-C1-C4alkyl, or the compounds of formula XX

in which Z6means oxygen or N-R110where R110represents a group of the formula

in which R111and R112independently of one another represent cyano, hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-C6alkenyl, aryl, phenyl or heteroaryl or substituted C1-C3the alkyl, C1-C3haloalkyl, C1-C3alkoxygroup, C1-C3/sub> haloalkoxy, halogen, cyano or nitro-group is phenyl, aryl or heteroaryl,

or the compounds of formula XXI

in which Z7means, sulfur, S=O, SO2or CH2, R114and R114independently of one another denote hydrogen, halogen or C1-C4alkyl, W2and W3independently from each other mean CH2COOR115or COOR0115or together signify a group of the formula -(CH2)C(O)-O-C(O)-(CH2)-, with R115and R0115independently of one another denote hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C6quinil, C3-C6cycloalkyl, C1-C4haloalkyl, a metal cation or ammonium,

or the compounds of formula XXII

in which R119and R120independently of one another denote hydrogen, halogen or C1-C4haloalkyl, R121means hydrogen, C1-C4alkyl, C3-C4alkenyl, C3-C4quinil, C1-C4haloalkyl, C3-C6cycloalkyl, a metal cation or ammonium, Z8means N, CH, C-F or C-Cl and W4means a group of the formula

where R122and R123independently of one another denote hydrogen or C1-C4alkyl, and R124and R 125independently of one another denote hydrogen or C1-C4alkyl, or the compounds of formula XXIII

in which R126means hydrogen, cyano, halogen, C1-C4alkyl, C3-C6cycloalkyl, C1-C4alkoxygroup, C1-C4alkoxycarbonyl, C1-C4alkylthiomethyl, -NH-R128, -C(O)NH-R0128, aryl or heteroaryl or substituted C1-C3the alkyl, C1-C3haloalkyl, C1-C3alkoxygroup, C1-C3haloalkoxy, halogen, cyano or nitro-group is aryl or heteroaryl, a R127means hydrogen, cyano, a nitro-group, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4thioalkyl, with R128and R0128independently of one another denote C1-C4alkyl, C1-C4haloalkyl, C3-C4alkenyl, C3-C4quinil, C3-C4cycloalkyl, aryl or heteroaryl or substituted C1-C3the alkyl, C1-C3haloalkyl, C1-C3alkoxygroup, C1-C3haloalkoxy, halogen, cyano or nitro-group is aryl or heteroaryl, formyl, C1-C4alkylaryl or C1-C4alkylsulfonyl,

or with the organisations of formula XXIV

in which R129and R130independently of one another denote hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, mono-C1-C8- or di-C1-C8alkylamino, C3-C6cycloalkyl, C1-C4thioalkyl, phenyl or heteroaryl, R131has the same meaning as R129and additionally IT means, NH2, halogen, CI-C1-C4aminoalkyl, C1-C4allylthiourea, C1-C4alkylsulfonyl or C1-C4alkoxycarbonyl, R132has the same meaning as R129and additionally means a cyano, a nitro-group, carboxyl, C1-C4alkoxycarbonyl, di-C1-C4aminoalkyl, C1-C4allylthiourea, C1-C4alkylsulfonyl, SO2-OH, ISO-C1-C4aminoalkylsilane or C1-C4alkoxycarbonyl, R133has the same meaning as R129and additionally IT means, NH2, halogen, CI-C1-C4aminoalkyl, pyrrolidin-1-yl, piperidine-1-yl, morpholine-1-yl, C1-C4allylthiourea, C1-C4alkylsulfonyl, C1-C4alkoxycarbonyl, fenoxaprop, NATEXPO, phenylaminopropyl, benzoyloxy or phenylsulfonylacetate,

or connection f is rmula XXV

in which R134means hydrogen, C4alkyl, C1-C4haloalkyl, C2-C4alkenyl, C2-C4quinil or C1-C4alkoxy-C1-C4alkyl, R135means hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxygroup, a R136means hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl or C1-C4alkoxygroup, provided that R135and R136at the same time do not represent a hydrogen

or the compounds of formula XXVI

in which R143means hydrogen, a cation of an alkali metal, alkaline earth metal, sulfone or ammonium or ethyl,

or the compounds of formula XXVII

in which R144and R145independently of one another denote hydrogen, C1-C6alkyl, C2-C6alkenyl, C2-C6quinil or C3-C6cycloalkyl, R146means hydrogen, halogen, C1-C4alkyl, C1-C6haloalkyl or C1-C6haloalkoxy, R147means hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4haloalkoxy, C1-C4Alki is tigroup, C1-C4alkoxycarbonyl or nitrogroup, n1means 0, 1, 2 or 3 and m is 1 or 2,

or the compounds of formula XXVIII

in which R148means hydrogen, C1-C6alkyl, C1-C6alkoxygroup, C1-C6allylthiourea, C3-C8cycloalkyl, phenyl, phenyl-C1-C6alkyl or heteroaryl, while these groups may be substituted with halogen, a cyano, a nitro-group, amino group, hydroxy-group, carbonyl, carboxyla, formyl, carbonamide or sulfonamide, R149means hydrogen, C1-C6alkyl or C1-C4haloalkyl, R150in each case independently denotes hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, cyano, a nitro-group, formyl or carboxyl, R151means hydrogen, C1-C6alkyl or C1-C4haloalkyl, R152in each case independently denotes hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4allylthiourea, C1-C4alkylsulfonyl, cyano, a nitro-group, formyl or carboxyl, means 0, 1 or 2 and p is 0, 1 or 2,

or is soedineniya formula XXIX

in which R159means hydrogen, formyl, C1-6alkylsulphonyl,1-6alkenylboronic,1-6alkenylboronic,1-6alkoxycarbonyl,1-6alkylthiomethyl,3-8cycloalkylcarbonyl, phenyl-C1-6alkylsulphonyl, phenylcarbinol,1-6alkylsulfonyl, C1-6alkanesulfonyl or phenylsulfonyl, these hydrocarbon groups may be substituted by one or more halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl,

R153means hydrogen, C1-6alkyl, C1-6alkenyl,1-6quinil,3-8cycloalkyl, formyl, C1-6alkylsulphonyl,1-6alkenylboronic,1-6alkenylboronic,1-6alkoxycarbonyl,1-6alkylthiomethyl,3-8cycloalkylcarbonyl,1-6alkylsulfonyl, C1-6alkanesulfonyl or phenylsulfonyl, these hydrocarbon groups may be substituted by one or more halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl,

R154means hydrogen, C1-6alkyl, C1-6alkenyl,1-6quinil,3-8cycloalkyl, formyl, C1-6alkylsulphonyl,1-6alkenylboronic,1-6alkenylboronic,1-6al is oxycarbonyl, With1-6alkylthiomethyl,3-8cycloalkylcarbonyl,1-6alkylsulfonyl, C1-6alkanesulfonyl or phenylsulfonyl, these hydrocarbon groups may be substituted by one or more halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl,

R155, R156, R157and R158independently of one another denote hydrogen, halogen, amino, C1-3alkylamino,1-6dialkylamino, the hydroxy-group, a cyano, a nitro-group, formyl, carboxyl,1-6alkoxygroup,1-6haloalkoxy,1-6alkylsulphonyl,1-6alkoxycarbonyl,1-6alkyl, C1-6haloalkyl,1-6alkenyl or1-6quinil or

R153and R158together with the ring atoms to which they are attached, form a five - or six-membered partially saturated or unsaturated cycle which may contain up to 2 identical or different heteroatoms selected from the group comprising oxygen, sulfur and nitrogen, while this cycle may be replaced by acousticom. Proposed in the invention means preferably contain herbicide-antagonistically effective amount of a safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV or XXV.

Proposed in the invention means with the villages of the active herbicide action preferably contain herbicide-antagonistically effective amount of any compound of the formula X

in which R37means hydrogen, C1-C8alkyl or substituted C1-C6alkoxygroup or3-C6alkenylacyl1-C8alkyl, and X6means hydrogen or chlorine,

either the compound of formula XI

in which E denotes nitrogen or Metin, R38means-CCl3, phenyl or substituted by halogen phenyl, R39and R40independently of one another denote hydrogen or halogen, a R41means1-C4alkyl,

either the compound of formula XII

in which R44and R45independently of one another denote hydrogen or halogen, and R46, R47and R48independently from each other mean With1-C4alkyl.

Above for compounds of formula I preferred options fair in the case of mixtures of compounds of the formula I with antidotes of formula X-XVIII. The preferred proposed in the invention means contain a safener selected from the group comprising the compound of formula Ha

formula Xb

and formula XIa

Other preferred compounds of formulas X, XI and XII are also presented below in tables 9, 10 is 11.

Table 9:

The compounds of formula X
Conn. No.X6R37
9.01Cl-CH(CH3)-C5H11-n
9.02Cl-CH(CH3)-CH2OCH2CH=CH2
9.03ClH
9.04ClC4H9-n

Preferred compounds of formula XI are presented below in table 10.

Table 10:

The compounds of formula XI
Conn. No.R41R38R39R40E
10.01CH3phenyl2-ClNSN
10.02CH3phenyl2-Cl4-ClSN
10.03CH3phenyl2-FNSN
10.04CH32-chloro who Anil 2-FNSN
10.05With2H5CCl32-Cl4-ClN
10.06CH3phenyl2-Cl4-CF3N
10.07CH3phenyl2-Cl4-CF3N

Preferred compounds of formula XII are presented below in table 11.

Table 11:

The compounds of formula XII
Conn. No.R46R47R48R44R45
11.01CH3CH3CH32-Cl4-Cl
11.02CH3With2H5CH32-Cl4-Cl
11.03CH3With2H5With2H52-Cl4-Cl

Preferred compounds of formula XIII are presented below in table 12 in the form of compounds of formula XIIIa.

Table 12:

The compounds of formula XIIIa
Conn. No.And2R51
12.001H
12.002H
12.003CH3
12.004CH3

Preferred compounds of formula XIV are presented below in table 13.

Table 13:

The compounds of formula XIV
Conn. No.R56R57R56+R57
13.001CH2=SNSN2CH2=SNSN2-

Conn. No.R56R57R56+R57
13.002--
13.003--
13.004--
13.005--
13.006--
13.007--
13.008--

Preferred compounds of formula XV are presented below in table 14.

Table 14:

The compounds of formula XV
Conn. No.R80R79
14.01NCN
14.02ClCF3

Preferred compounds of formula XVI are presented below in table 15.

Table 15:

The compounds of formula XVI
Conn. No.R81
15.01N
15.02 CH3

Preferred compounds of formula XVII are presented below in table 16 in the form of compounds of formula XVIIa.

Table 16: Compounds of formula XVIIa
Conn. No.R82Z4Vr
16.001NO1
16.002NO1
16.003NO1

S
Conn. No.R82Z4Vr
16.004NO1
16.005NCH21
16.006NCH21
16.007N1
16.008NS1
16.009NNCH31
16.010NNCH31
16.011NNCH31
16.012NO1
16.013NS1

Preferred compounds of formula XVII are presented below in table 17 in the form of compounds of formula XVIIb.

Table 17:

The compounds of formula XVIIb
Conn. No.UR82Z4
17.001ON

Conn. No.UR82Z4
17.02 OH
17.003O5-Cl
17.004CH2H
17.005CH2H
17.006CH2H
17.007NH5-Cl
17.008NH5-Cl
17.009NHH
17.010NHH
17.011NCH3H
17.012NCH3H

Preferred compounds of formula XVII are presented below in table 18 in the form of compounds of formula XVIIc.

Table 18:

The compounds of formula XVIIc

Conn. No.UVrW1Z4R82
18.001OC=O1CH2N
18.002OC=O1CH2N
18.003CH2C=O1CH2N
18.004CH2C=O1CH2N
18.005CH2CH21C=ON
18.006CH2CH21C=ON
18.007NCH3C=O1CH2N

Preferred with the organisations of the formula XVII are presented below in table 19 in the form of compounds of formula XVIId.

Table 19:

The compounds of formula XVIId
Conn. No.R82W1
19.0016-Cl
19.0026-Cl
19.003N
19.004N

Conn. No.R82W1
19.005H

Preferred compounds of formula XVIII are presented below in table 20.

Table 20:

The compounds of formula XVIII
Conn. No.R103R104R105R106
20.01CH3NcyclopropylN
20.02CH3 2H5cyclopropylN
20.03CH3cyclopropylWith2H5N
20.04CH3CH3NN
20.05CH3CH3cyclopropylN
20.06CH3Och3Och3N
20.07CH3CH3Och3N
20.08CH3Och3CH3N
20.09CH3CH3CH3N
20.10With2H5CH3CH3N
20.11With2H5Och3Och3N
20.12NOch3Och3N
20.13NCH3CH3N
20.14C2H5NNsub> 3
20.15NNNCH3
20.16CH3NNCH3
20.17CH3CH3NCH3

From among the compounds of formula XXVIII are preferred compounds in which R148means hydrogen, C1-C6alkyl, C3-C8cycloalkyl or phenyl, while these groups may be substituted with halogen, a cyano, a nitro-group, amino group, hydroxy-group, carbonyl, carboxyla, formyl, carbonamide or sulfonamide, R149means hydrogen, R150in each case independently denotes hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4allylthiourea, a cyano, a nitro-group or formyl, R151means hydrogen and R152in each case independently denotes hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxygroup, C1-C4allylthiourea, a cyano, a nitro-group or formyl.

The most preferred compounds of formula XXVIII are compounds from the group including

2-methoxy-N-[4-(2-methoxybenzenesulfonyl)phenyl]azeta the ID,

N-[4-(2-methoxybenzenesulfonyl)phenyl]cyclopropanecarboxamide,

N-[4-(2-methoxybenzenesulfonyl)phenyl]cyclobutanecarboxylic,

N-[4-(2-chlorobenzenesulfonyl)phenyl]cyclopropanecarboxamide,

N-[4-(2-chlorobenzenesulfonyl)phenyl]acetamide", she

N-[4-(2-cryptomaterial)phenyl]acetamide", she

N-[4-(2-triftoratsetilatsetonom)phenyl]cyclopropane-carboxamide,

N-[4-(2-cryptomaterial)phenyl]cyclopropane-carboxamide,

N-[4-(2-cryptomaterial)phenyl]cyclobutanecarboxylic and

N-[4-(2-triftoratsetilatsetonom)phenyl]ndimethylacetamide.

Among the compounds of formula XXIX are preferred compounds in which R159means hydrogen, formyl, C1-6alkylsulphonyl, C1-6alkenylboronic, C1-6alkenylboronic, C1-6alkoxycarbonyl, C1-6alkylthiomethyl, C3-8-cycloalkylcarbonyl, phenyl-C1-6alkylsulphonyl or phenylcarbinol, these hydrocarbon residues may be substituted by one or more halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl, R153means hydrogen, C1-6alkyl, C1-6alkenyl, C1-6quinil, formyl, C1-6alkylaryl or C1-6alkoxycarbonyl, these hydrocarbon residues may be substituted by one or a few is Kimi halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl, R154means hydrogen, C1-6alkyl, C1-6alkenyl, C1-6quinil, formyl, C1-6alkylaryl or C1-6alkoxycarbonyl, these hydrocarbon residues may be substituted by one or more halogen atoms, a cyano, a nitro-group, amino group, methoxy group, ethoxypropane or phenyl, R155, R156, R157and R158independently of one another denote hydrogen, halogen, a cyano, a nitro-group, formyl, carboxyl, C1-6alkoxygroup, C1-6haloalkoxy, C1-6alkylsulphonyl, C1-6alkoxycarbonyl, C1-6alkyl or C1-6haloalkyl or R153and R158together with the ring atoms to which they are attached, form a five - or six-membered partially saturated or unsaturated cycle which may contain up to 2 identical or different heteroatoms from the group comprising oxygen, sulfur and nitrogen, while this cycle may be substituted by one acousticom.

More preferred compounds of formula XXIX are distinguished by the fact that R159means hydrogen, formyl, C1-6alkylsulphonyl, C1-6alkenylboronic, C1-6alkenylboronic, C1-6alkoxycarbonyl, C1-6alkylthiomethyl, C3-8-cycloalkylcarbonyl refererer, R153means hydrogen, C1-6alkyl, C1-6alkenyl, C1-6quinil, formyl, C1-6alkylaryl or C1-6alkoxycarbonyl, R154means hydrogen, C1-6alkyl, C1-6alkenyl, C1-6quinil, formyl, C1-6alkylaryl or C1-6alkoxycarbonyl, R155, R156, R157and R158independently of one another denote hydrogen, halogen, a cyano, a nitro-group, formyl, C1-6alkyl, C1-6haloalkyl, C1-6alkoxygroup or C1-6haloalkoxy or R153and R158together with the ring atoms to which they are attached, form a five - or six-membered partially saturated or unsaturated cycle which may contain up to 2 identical or different heteroatoms from the group comprising oxygen, sulfur and nitrogen, while this cycle may be substituted by one acousticom.

The most preferred compounds of formula XXIX are compounds from the group including

4-hydroxy-1-methyl-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

1-ethyl-4-hydroxy-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

6-hydroxy-5-(1H-tetrazol-5-carbonyl)-1,2-dihydropyrrolo[3,2,1-.ij.]the quinoline-4-one,

3-(1-acetyl-1H-tetrazol-5-carbonyl)-4-hydroxy-1-methyl-1H-quinoline-2-it,

6-chloro-4-hydroxy-1-methyl-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

6-fluoro-4-hydroxy-1-methyl-3-(1H-tetrazol-carbonyl)-1H-quinoline-2-it,

4-hydroxy-1,6-dimethyl-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

4-hydroxy-6-methoxy-1-methyl-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

4-hydroxy-6-methoxy-1-methyl-3-(1H-tetrazol-5-carbonyl)-1H-quinoline-2-it,

1-methyl-2-oxo-3-(1H-tetrazol-5-carbonyl)-1,2-dihydroquinoline-4-silt ester of acetic acid and

1-methyl-2-oxo-3-(1H-tetrazol-5-carbonyl)-1,2-dihydroquinoline-4-silt ether of 2,2-dimethylpropionic acid.

The present invention relates also to a method of selective weed control in crops of useful plants, which consists in the fact that the useful plants, seeds or cuttings or area of their cultivation simultaneously or separately treated herbicide effective amount of a herbicide of formula I and herbicide-antagonistically effective amount of a safener of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, preferably of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII. Cultivated plants, protecting them from the adverse effects of the above herbicides can provide the antidote of formula X, XI, XII, XIII, XIV, XV, XVI, XVII or XVIII, are, for example, cereals, cotton, soybeans, sugar beets, sugar cane cultivated on plantations crops, canola, corn and rice, primarily corn and cereals. Under cultivated plants should also be understood Rast is tion, with the traditional methods of breeding or genetic engineering was developed tolerance to herbicides, respectively, to different classes of herbicides.

Weeds that are struggling can be both monocotyledonous and dicotyledonous weed plants, such monocotyledonous weeds, as Avena, Agrostis, Phalaris, Lolium, Bromus, Alopecurus, Setaria, Digitaria Brachiaria, Echinochloa, Panicum, Sorghum hal./the bic., Rottboellia, Cyperus, Brachiaria, Echinochloa, Scirpus, Monochoria, Sagittaria, and Stellaria, such a dicotyledonous weed plants such as Sinapis, Chenopodium, Galium, Viola, Veronica, Matricaria, Papaver, Solanum Abutilon, Sida, Xanthium, Amaranthus, Ipomoea and Chrysanthemum.

To cultivated areas include land already germinated or grown cultivated plants or land, sowed these seeds of cultivated plants, as well as soil that is allocated to the cultivation of these crops.

The antidote of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, depending on the purpose of application can be used for pre-treatment of seed or planting material of cultivated plants (seed or cuttings) either before or after sealing the seed in the soil. However, the processing of the antidote can be performed individually or together with the herbicide after emergence of the plants. Thus, treatment of plants or the planting is on material antidote in principle can be performed regardless of the time of herbicide treatment. However, plants can be treated and at the same time means both the herbicide and the antidote (for example, when used in the form of a tank mixture). The ratio between the applied quantities of antidote and herbicide largely depends on the type of processing. For example, when processing fields, which may consist of a tank mix herbicide in combination with a safener, or in separate introduction of safener and herbicide, the ratio between the amount of herbicide and the number of antidote is usually from 100:1 to 1:10, preferably from 20:1 to 1:1. Generally, the consumption rate of the antidote when a field is from 0.001 to 1.0 kg/ha, preferably from 0.001 to 0.25 kg/ha

The rate of application of herbicide is usually from 0.001 to 2 kg/ha, preferably, however, 0.005 to 0.5 kg/ha

The treatment proposed in the invention means can be made in all conventional agricultural methods, such as predsjedava processing, post-harvest processing and seed dressing.

When the seed treatment rate of application of the antidote is usually from 0.001 to 10 g per kg of seed, preferably from 0.05 to 2 g per kg seeds. If the antidote is carried out in liquid form shortly before sowing during the swelling of the seeds, it is advisable to use solutions antidote concentration dei is adequate substances from 1 to 10000, preferably from 100 to 1000 ppm million

To handle the antidotes of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX some antidotes in combination with herbicides of formula I, it is expedient to revise together with usually used in cooking techniques preparative forms of auxiliary substances to ensure that proper preparations, for example mulgirigala concentrates, pastes for obmazyvanija, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, Farrukh Dustov, granules or microcapsules.

Such formulation are described, for example, in WO 97/34485 on p.9-13. Such formulations of get known method, for example by homogeneous mixing and/or grinding the active substances with solid or liquid excipients used in the composition of preparative forms, for example solvents or solid carriers. In addition, when receiving preparative forms optionally, you can use surface-active substances (surfactants). Examples suitable for this purpose solvents and solid carriers are described, for example, in WO 97/34485 on page 6.

As surface-active substances depending on what should be included in formulations of the active substance of the formula I used for the nonionic form, cationogenic and/or anionic surfactants and mixtures of surfactants with high emulsifying, dispersing and wetting properties. Examples suitable for this purpose anionic, nonionic and cationogenic surfactants are described in particular in WO 97/34485 on page 7 and 8. In addition, to obtain the proposed invention herbicide suitable means commonly used in the preparation technology preparative forms of surfactants, which are described in particular in "Me Cutcheon''s Detergents and Emulsifiers Annual", published by MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", publishing house Carl Hanser Verlag, München/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", T.I-III, published by Chemical Publishing Co., New York, 1980-81.

Herbicide compositions usually contain from 0.1 to 99 wt.%, especially from 0.1 to 95 wt.% active substances in the form of a mixture of compounds of formula I with compounds of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, from 1 to 99.9 wt.% solid or liquid excipients used in the formulation, and from 0 to 25 wt.%, first of all, from 0.1 to 25 wt.% Surfactants. If included in sale products preferred means in the form of concentrates, the end user usually uses diluted preparations.

Such funds may also contain other additives, such as stabilizers, for example optional epoxydecane vegetable oil (EPoX deroanne coconut oil, rapeseed oil or soybean oil), antispyware, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, as well as fertilizers or other active substances. To apply the antidotes of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX or containing means for protecting cultivated plants from the adverse effects of herbicides of the formula I are suitable various methods and techniques, such as described below.

I) seed Dressing

a) seed Treatment, make use of a prepared in the form of a wettable powder of the active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX by shaking in an appropriate vessel until uniform distribution of the drug on the surface of the seeds (dry etching). Use about 1 to 500 g of active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX (4 g to 2 kg of wettable powder) per 100 kg of seed.

b) seed Treatment emulgirujushchie concentrate of the active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX carried out according to the above described method a) (wet dressing).

b) seed Treatment is conducted by immersing the working solution, containing 100-1000 ppm million active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, 1-72 h and then the seeds if necessary, dried (wet etching by immersion).

Seed treatment or processing of germinated seeds are probably the preferred methods of processing, because such processing, the active substance is fully interacts with the target culture. The consumption rate of the antidote is usually from 1 to 1000 g, preferably from 5 to 250 g per 100 kg of seed material with the rate depending on the technique, allowing the addition of other active ingredients or micronutrients may differ from the specified concentration limits both in big, and the smaller side (repeat dressing).

II) a Treatment tank mixtures

In this case, use is brought to a liquid state, the mixture of antidote and herbicide (mutual quantitative ratio of the components is from 10:1 to 1:100), and the rate of application of herbicide is 0.005 to 5.0 kg per hectare. Processing such bukovymi mixtures is carried out before or after sowing.

III) Introducing into the seed furrow

The active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX as mulgirigala concentrate, wettable powder and granules contribute to open-sown seed furrow. After closing the seed furrow in the usual way spend redshadow processing herbicide.

IV) Controlled release of the active substance

The active substance of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX applied from a solution in mineral granular media or polymer granules (urea/formaldehyde) and dried. Then if necessary, you can apply an extra coating the granulate in the shell), which allows for a certain amount of time to release the active substance in dosed quantities.

The effectiveness of the proposed invention herbicide and inhibit the growth of plants containing herbicide effective amount of the compounds of formula I, as well as herbicide-antagonistically effective amount of the compounds of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, can be improved through the use of adjuvants that are added to the tank with the preparation for spraying. Such adjuvants may constitute, for example, nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationogenic surfactants, silicone surfactants, derivatives, mineral oils, surfactants, derivatives of vegetable oils with or without added surfactants, alkylated PR is spodnie oils of vegetable or mineral origin with surfactants and without them, fish oil and other animal oils, as well as their alkyl derivatives with surfactants and without them, naturally occurring higher fatty acid, preferably 8-28 carbon atoms, and derivatives thereof in the form of alilovic esters, organic acids containing aromatic cyclic system and one or more esters of carboxylic acids and their alkyl derivatives and, in addition, suspensions of polymers of vinyl acetate or copolymers of vinyl acetate and esters of acrylic acid. A mixture of individual adjuvants among themselves, as well as their use in combination with organic solvents can further increase efficiency.

As an example, nonionic surfactants can be called polyglycolether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and ALKYLPHENOLS, which can contain preferably from 3 to 30 glycolether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and from 6 to 18 carbon atoms in the alkyl fragment of ALKYLPHENOLS.

Other suitable nonionic surfactants are water-soluble, preferably containing from 20 to 250 etilenglikolevykh groups and from 10 to 100 propylenglykolether groups, the addition products of polyethylene oxide to polypropylenglycol, ethylenediaminetriacetic the Yu and alkylpolyethylenglycol preferably 1-10 carbon atoms in the alkyl chain. These compounds typically contain from 1 to 5 etilenglikolevykh links on one propilenglikole link.

As other examples of nonionic surfactants should mention also nonylphenolethoxylates, polyglycidyl ether of castor oil, adducts of polypropylene-polyethylene oxide, tributyltinoxide, polyethylene glycol and octylphenoxypolyethoxyethanol.

In addition, you can also use esters of fatty acids and polyoxyethylenesorbitan, such as polyoxyethylenesorbitan.

Among the anionic surfactants are preferred primarily alkyl sulphates, alkyl sulphonates, alkylarylsulphonates, alkylated phosphoric acid, and their ethoxylated derivatives. Alkyl residues typically contain from 8 to 24 carbon atoms.

Preferred nonionic surfactants are known under the following trade names: polyoxyethylene-cocoalkylamine (for example, AMIET®105 (firm Kao Co.)), polyoxyethylene-oleylamine (for example, AMIET®415 (firm Kao Co.)), nonylphenolethoxylates, polyoxyethylene-stearylamine (for example, AMIET®320 (firm Kao Co.)), N-polyethoxyethanol (for example, GENAMIN®(the firm Hoechst AG)), N,N,N',N'-Tetra(politicsimprovement)ethylendiamine (for example, TERRONIL** and TETRONIC®(BASF Wyandotte Corp.)), BRIJ®(firm Atlas Chemicals), ETHYLAN® CD and ETHYLAN®D (company Diamond Shamrock), GENAPOL®C, GENAPOL®O, GENAPOL®S and GENAPOL®X080 (firm Hoechst AG), EMULGEN®104P, EMULGEN®109P and EMULGEN®408 (firm Kao Co.), DISTY®125 (firm Geronazzo), SOPROPHOR®CY 18 (firm Rhône Poulenc S.A.), NONISOL®(the company Ciba-Geigy), MRYJ®(the company ICI), TWEEN®(the company ICI), EMULSOGEN®(the firm Hoechst AG), AMIDOX®(firm Stephan Chemical Co.), ETHOMID®(firm Armak Co.), PLURONIC®(BASF Wyandotte Corp.), SOPROPHOR®461P (firm Rhône Poulenc S.A.), SOPROPHOR®496/P (firm Rhône Poulenc S.A.), ANTAROX FM-63 (firm Rhône Poulenc S.A.), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (firm Osi Specialities).

If cationogenic surfactants it is first and foremost about the salts of Quaternary ammonium bases, which as N-substituents contain at least one alkyl residue with 8-22 C-atoms and the other substituents are lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl residues. As such salts are the preferred halides, methylsulfate or ethylsulfate, such as steartrimonium or benilde(2-chloroethyl)ethylammonium.

The oils used are either mineral or natural. Natural oils can also be of animal or vegetable origin is of an unforgettable. As animal oils are used mainly derived beef fat (tall oil)and fish oil (for example, fat sardines) and their derivatives. Vegetable oils are typically oil from seeds of different origin. As an example, the most commonly used vegetable oils can be called coconut, rapeseed or sunflower oil and their derivatives.

The content of oil additives in the proposed invention the agent is usually from 0.01 to 2% in terms of working solution. Oil additive can, for example, be added in the desired concentration in the tank with the preparation for spraying after preparation of the working solution.

Preferred oil additives to offer in the invention means are oil of vegetable origin, for example rapeseed oil or sunflower oil, alkalemia esters of oils of vegetable origin, such as methyl derivatives, or mineral oil.

The most preferred oil additives contain alkalemia esters of higher fatty acids (C8-C22), especially methyl derivatives of C12-C18fatty acids, such as methyl ester of lauric acid, palmitic acid and oleic acid. Such esters are known as meilleur (CAS 111-82-0), metralleta (CAS 112-39-0) and methyl oleate(CAS 112-62-9).

The efficiency of oil additives can be improved by using them in combination with surfactants, such as nonionic, anionic or cationogenic surfactant. Examples suitable for this purpose anionic, nonionic and cationogenic surfactants are described in WO 97/34485 on page 7 and 8.

Preferred surfactants are anionic surfactants of the type dodecylbenzensulfonate, primarily their calcium salts, and nonionic surfactants of the type of ethoxylates of fatty alcohols. The preferred ethoxylated C12-C22fatty alcohols with a degree of amoxilonline from 5 to 40. Examples of commercially available preferred surfactants are the products of type Genapol (company Clariant AG, Muttenz, Switzerland). The concentration of surfactants in terms of the total amount of additive is usually from 1 to 30 wt.%.

Examples of oil additives consisting of mixtures of oils, respectively, mineral oils or derivatives thereof with surfactants are products Edenor ME SU®, Emery 2231®(firm Henkel Tochtergesellschaft Cognis GMBH, Germany), Turbocharge®(firm Zeneca Agro, young Stoney Creek, Ontario, Canada) or most preferably Actipron®(company BP Oil UK Limited, UK).

In addition, to improve the efficiency of the mixture of the oil with surfactant additives provides the addition thereto of an organic solvent. Suitable for this purpose solvents are, for example, Solvesso®(company ESSO) or Aromatic Solvent®(company Exxon Corporation). The concentration of these solvents may be from 10 to 80 wt.% of the total mass.

Such oil supplements, which are described, for example, in US 4834908, most preferred for use in the composition proposed in the invention of money. The most preferred oil additive known under the name MERGE®produced by BASF Corporation and in General are described, for example, in US 4834908, column 5, as an example, SOS-1. Another preferred according to the invention with an oil additive is the product SCORE®(Novartis Crop Protection Canada).

Usually used in cooking techniques preparative forms and adjuvants of surfactants, oils, especially vegetable oils, their derivatives such as alkylated fatty acids and their mixtures, for example, preferably anionic surfactants, such as alkylated phosphoric acids, alkyl sulphates and alkylarylsulfonate, as well as higher fatty acids, which can also be used in the proposed invention the means and prepared from them in tanks solutions for spraying, described in particular in "Mc Cutcheon''s Detergents and Emulsifiers Annual", published by MC Publishing Corp., Ridgewood New Jersey, 1998, H. Stache, "Tensid-Taschenbuch", publishing house Carl Hanser Verlag, München/Wen, 1990, M. and J. Ash, "Encyclopedia of Surfactants", T.I-IV, published by Chemical Publishing Co., New York, 1981-89, G. Kapusta, "A Compendium of Herbicide Adjuvants", Southern Illinois Univ., 1998, L. Thomson Harvey, "A Guide to Agricultural Spray Adjuvants Used in the United States"published by Thomson Pubns., 1992.

Below are the compounds most preferred compositions according to the invention (%=% by weight):

Mulgirigala concentrates:
the mixture of active substances:1-90%, preferably 5-20%
surfactant:1-30%, preferably 10-20%
carrier liquid:5-94%, preferably 70-85%
Dusty:
the mixture of active substances:0.1 to 10%, preferably 0.1 to 5%
carrier liquid:of 99.9 to 90%, preferably about 99.9 to 99%
Suspension concentrates:
the mixture of active substances:5-75%, preferably 10-50%
water:94-24%, preferably 88-30%
surfactant:1-40%, preferably 2-30%
Wettable powders:
the mixture of active substances:0.5 to 90%, preferably 1-80%
surfactant: 0.5 to 20%, preferably 1-15%
solid carrier:5-95%, preferably 15-90%
Granules:
the mixture of active substances:0.1 to 30%, preferably 0.1 to 15%
solid carrier:of 99.5 to 70%, preferably 97-85%

Below the invention is illustrated in the examples, not limiting its scope.

Examples of compositions in the form of mixtures of herbicides of formula I and antidotes of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX (%=wt.%)

F 1. Mulgirigala concentratesa)b)in)g)
the mixture of active substances5%10%25%50%
Sa-dodecylbenzensulfonate6%8%6%8%
polyglycidyl ether of castor oil (36 mol of EO)4%-4%4%
polyglycolic ether op (7-8 mol of EO)-4%-2%
cyclohexanone--10%20%
the mixture aromatic. hydrocarbons, C 9-C1285%78%55%16%

From such concentrates by dilution with water can be prepared emulsions of any desired concentration.

F2. Solutionsa)b)in)g)
the mixture of active substances5%10%50%90%
1-methoxy-3-(3-methoxypropane)propane-20%20%-
the polyethylene glycol 400 MM20%10%--
N-methyl-2-pyrrolidone--30%10%
the mixture aromatic. hydrocarbon, C9-C1275%60%--

Such solutions are suitable for application in the form of tiny droplets.

F3. Wettable powdersa)6)in)g)
the mixture of active substances5%25%50%80%
Na-ligninsulfonate4%-3% -
Na-lauryl2%3%-4%
Na-diisobutyldimethoxysilane-6%5%6%
polyglycolic ether op (7-8 mol of EO)-1%2%-
highly dispersed silicic acid1%3%5%10%
kaolin88%62%35%-

The active ingredient is thoroughly mixed with additives and thoroughly ground in a suitable for this purpose mill. In this way receive wettable powders, of which the dilution water can be obtained suspensions of any desired concentration.

F4. Pellets in the shella)b)in)
the mixture of active substances0,1%5%15%
highly dispersed silicic acid0,9%2%2%
neorganic. media99,0%93%83%
(⊘ 0,1-1 mm), for example, caso3or SiO2

D. actuuse substance is dissolved in methylene chloride, sprayed on the media and finally the solvent is evaporated in vacuum.

F5. Pellets in the shella)b)in)
the mixture of active substances0,1%5%15%
polyethylene glycol 200 MM1,0%2%3%
highly dispersed silicic acid0,9%1%2%
neorganic. media98,0%92%80%
(⊘ 0,1-1 mm), for example, caso3or SiO2

Finely ground active substance is applied in the mixer to wet glycol carrier. In this way receive a dust free pellets in the shell.

kaolin
F6. Extruded granulesa)b)in)g)
the mixture of active substances0,1%3%5%15%
Na-ligninsulfonate1,5%2%3%4%
carboxymethylcellulose1,4%2%2%2%
97,0%93%90%79%

The active substance is mixed with additives, crushed and moistened with water. This mixture ekstragiruyut and finally dried in the air stream.

F7. Dustya)b)in)
the mixture of active substances0.1%1%5%
talc39,9%49%35%
kaolin60,0%50%60%

Ready-to-use dusty obtained by mixing the active ingredient with the carriers and grinding in a suitable for this purpose mill.

F8. Suspension concentratesa)6)in)g)
the mixture of active substances3%10%25%50%
ethylene glycol5%5%5%5%
polyglycidyl ether of Nonylphenol (15 moles EO)-1%2%-
Na-ligninsulfonate3%3%4%5%
carboxymethylcellulose1%1%1%1%
37%aqueous formaldehyde solution0,2%0,2%0,2%0,2%
silicone oil emulsion0,8%0,8%0,8%0,8%
water87%79%62%38%

Finely ground active substance until homogeneity is mixed with additives. In this way receive a suspension concentrate from which the dilution water can be obtained suspensions of any desired concentratie.

In practice it is often more expedient separately prepare the formulations based on the active substance of the formula I and the components of the mixture of the formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX, and then merge these compounds in water shortly before use in the respective treatment device in the desired proportions to obtain the so-called "tank mixtures".

The ability of the antidotes of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX to protect cultivated plants from phyto-toxic action of herbicides of formula I is illustrated in the following examples.

Biological example 1: Protective on the op perate as antidote

Pilot plants are grown in plastic pots under greenhouse conditions until stage four leaves. At this stage of the experimental plants treated only with the herbicide and herbicide mixtures with tested compounds, issleduemymi on their action as antidotes. The treatment is carried out with an aqueous suspension of the test compounds, obtained from a 25%wettable powder (example F3, b)), with a flow rate of 500 l of water/ha 2-3 weeks after treatment as a percentage appreciate phyto-toxic effect of the herbicide on the crop plants, such as corn and grains. 100% corresponds to the total loss experienced by plants and 0% corresponds to the total absence of phyto-toxic action.

Obtained in this experiment the results indicate that the use of compounds of formula X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII or XXIX can significantly reduce damage to cultivated plants with the herbicide of the formula I. the following table B5 as an example, presents some of the data obtained in this experiment the results.

Conn no.1.01 (60 g/ha)+
Table 5:

Post-harvest action proposed in the invention a mixture of herbicide to antidote
Experienced plantConn. No. 1.01 (60 g/ha)
Conn. No. 11.03 (15 g/ha)
Barley200
Agrostis7070
Alopecurus7080
Lolium7070

The figures in table B5 data suggest that individually compound No. 1.01 has on barley invalid phyto-toxic effect, constituting 20%. The degree of suppression of weeds Agrostis, Alopecurus and Lolium is satisfactory.

In contrast, proposed in the invention is a mixture consisting of herbicide No. 1.01 and antidote No. 11.03, not having on a cultivated plant no phyto-toxic action. When this herbicide effects on weeds not only remains at a comparable level, but even that is an unexpected fact, reinforced by the Alopecurus (80% vs. 70% when processing only herbicide No. 1.01).

The same results were obtained with the application of the compounds mentioned in the examples F1, F2 and F4-F8 formulations.

The compound of formula I allow it to mix with a variety of other known herbicides with the achievement of the relevant benefits. So, for example, can significantly expand the range destroy weeds, and in many cases even increase the selectivity for useful plants. When this special is the value are primarily a mixture of compounds of formula I with at least one of the following herbicides (Russian names of herbicides, if they exist, are given in accordance with the Handbook "Pesticides and plant growth regulators", Melnikov N.N. and other M: Chemistry, 1995, and in accordance with the Handbook "New pesticides", Belan S.R., and others, Publishing House "Grail", 2001):

with herbicides from the class phenoxybenzamine acids, such as diclofop-methyl, fluazifop-P-butyl, hisamoto-P-ethyl, prophetarum, clodinafop-P-propargyl, cyhalofop-butyl, fenoxaprop-P-ethyl, haloxyfop-methyl or haloxyfop-ethoxyethyl;

with herbicides from the class hydroxyamino, such as sethoxydim, aloxide, clethodim, cycloxydim, tepraloxydim, tralkoxydim or butoxide;

with herbicides from the class of sulfonylureas, such as amidosulfuron, azimsulfuron, enculture-methyl, chlorimuron-ethyl, chinaculture, chlorsulfuron, chlorimuron, cycloaliphatic, atomiculture-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron, imazosulfuron, iodosulfuron (CAS RN 144550-36-7 and 185119-76-0), metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, pyrazosulfuron-ethyl, sulfosulfuron, rimsulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, prosulfuron, flucarbazone or tritosulfuron (CAS RN 142469-14-5);

with herbicides from the class imidazolinones, such as imazethapyr, imazamethabenz, imazamethabenz, imazighen, imaza the ACS or imazapyr;

with herbicides from the class of pyrimidines, such as pyrithiobac sodium, Perminova, bispyribac-sodium;

with herbicides from the class of triazines, such as atrazine, Simazine, simetryn, terbutryn or terbutylazine;

with herbicides from the class of ureas, such as Isoproturon, chlortoluron, Diuron, damron, fluometuron, linuron or methabenzthiazuron;

with herbicides from the class Provodnik phosphonic acids, such as glyphosate, glufosinate, sulfosate or phosphinotricin;

with herbicides from the class PPO, such as nitrogen, bifenox, acifluorfen, lactofen, oxyfluorfen, idoxifene, fluoroglycofen, fomesafen, galasoft, azafenidin (CAS RN 68049-83-2), bestindian (CAS RN 158755-95-4), butoverall (known from US 5183492, CAS RN 158755-95-4), carfentrazone-ethyl, cynodon-ethyl (CAS RN 142891-20-1), flumiclorac-pentyl, flumioxazin, fluthiacet-methyl, oxadiargyl, oxadiazon, phenoxazone, sulfentrazone, flatlet (CAS RN 174514-07-9) or pyraflufen-ethyl;

with herbicides from the class of chloroacetanilides, such as alachlor, acetochlor, butachlor, dimethachlor, dimethenamid, S-dimethenamid, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, tanishlar or Itemid (CAS RN 106700-29-2);

with herbicides from the class PHENOXYACETIC acids, such as 2,4-D, fluroxypyr, 2M-4 (MSRA), 2M-HP (MSRR), 2M-HM (MSRV), trichlorfon or mecoprop-P;

with herbicides from the class tries nonow, such as hexazinone, metamitron or metribuzin;

with herbicides from the class of dinitroanilines, such as oryzalin, pendimethalin or trifluralin;

with herbicides from the class of azinones, such as ozone chloride or norflurazon;

with herbicides from the class of carbamates, such as chlorpropham, desmedipham, phenmedipham or propham;

with herbicides from the class of oxoazetidin, such as mefenacet or fluthiacet;

with herbicides from the class of thiolcarbamate, such as butyl, cycloate, diallate, EPTC, asbroker, molinet, prosulfocarb, thiobencarb or triallate;

with herbicides from the class of Solomatin, such as phentramin (CAS RN 158237-07-1) or cafestol;

with herbicides from the class of benzoic acids, such as dicamba or picloram;

with herbicides from the class of anilides, such as diflufenican or propanil;

with herbicides from the class of NITRILES, such as bromoxynil, dichlobenil or ioxynil;

with herbicides from the class of trions, such as sulcotrione, mesotrione (known from US 5006158), isoxaflutole or isoxaflutole;

with herbicides from the class of sulfonamides, such as flucarbazone (CAS RN 181274-17-9), procarbazine (CAS RN 145026-81-9), florasulam, dicloflam (CAS RN 145701-21-9), florasulam, flumetsulam or metosulam;

and with such herbicides as amitrol, belforest, bentazon, cinmetacin, clomazone, clopyralid, difenzoquat, ditio the Il, ethofumesate, fluorochloridone, indianian, isoxaben, oxacyclobutane, peridot, perinatal (CAS RN 40020-01-7), chinkara, hinnerk, tridiphane or planrep.

The above components of the mixture with the compound of the formula I is known, if not stated otherwise, reference to "The Pesticide Manual", 11th ed., 1997, WSRC. Such components are used in a mixture with the compound of the formula I, if necessary, may also be present in the form of esters or salts, represented, for example, in the Handbook "The Pesticide Manual", 11th ed., 1997, WSRC.

Below the invention is illustrated in the examples, not limiting its scope.

Examples retrieve

Example H1: Obtaining the compounds of formula

To a solution of 20 g of dimethyl 2-(2,6-dibromo-4-were)malonic acid (52,6 mmole) in 400 ml of toluene (after three vacuum degassing with argon) first type of 36.7 g (0,116 mole) of tributylstannyl, and then 2 g tetranitroaniline. Next, the reaction mixture is stirred for 9 hours at a temperature of 90-95°C. After filtration through Hyflo and concentration on a rotary evaporator, followed by chromatographic purification gain of 15.3 g of compound (8) in the form of a yellow oil, which was used without additional purification in the reaction at the next stage.

Example H2

152 g obtained in example H1 connection (8) hydronaut hydrogen over a palladium catalyst (charcoal as a carrier, 7 g of 5%Pd/C) in 160 ml of tetrahydrofuran at a temperature of 20-25°C. Upon completion of the hydrogenation product is filtered through Hyflo and the resulting filtrate concentrated on a rotary evaporator. In this way gain of 13.7 g of compound (9) in the form of yellow crystals with tPL47-49°C.

Example H3

To a suspension of 40 grams (0.15 mole) of the compound (4) in 1000 ml of xylene add 71,8 g (of 0.71 mole) of triethylamine and Tegaserod (four times in the vacuum with argon). Next, the yellow suspension is heated to a temperature of 60°C and stirred for 3 hours After that add to 42.5 grams (0.15 mole) of the compound (5) and for the continuous distillation of excess triethylamine and the resulting ethanol is heated to a temperature bath of 150°C. After 3 h the reaction mixture is cooled to a temperature of 40°and merge it into 500 ml of a mixture of ice and water. Then the reaction mixture with 100 ml of aqueous 1 n sodium hydroxide create an alkaline environment and the aqueous phase (containing the product), washed twice with ethyl ether, acetic acid. After two back washing the organic phase with an aqueous solution of 1 n sodium hydroxide aqueous phase combine remaining xylene is distilled off and the pH of the combined aqueous phases using 4 N. HCl set when cooled at 2-3. Drop down in the precipitated product is separated on a vacuum filter, the filter cake washed the Ute water, and then within a short period of time with hexane and then the precipitate is dried in vacuum over P2O5at a temperature of 60°S. This way get 34,6 g of compound (6) in the form of a light beige solid with tPL242-244° (Razlog.).

Example H4

It cooled down to 0°With a solution of 3 g (of 10.4 mmole) of the compound (6) and 1.6 g (15.8 mmole) of triethylamine in 100 ml of tetrahydrofuran, add a catalytic amount of 4-dimethylaminopyridine (DMAP). Then added dropwise of 1.57 g (13.0 mmol) of pivaloate (IRP-Cl). After 30 minutes stirring at a temperature of 0°With cooling stop and stirred for further 60 minutes and Then the reaction mixture was poured into a saturated aqueous solution of sodium chloride and the organic phase is separated. This organic phase is dried over magnesium sulfate, filtered and evaporated. After chromatographic purification and recrystallization from diethyl ether get 2,94 g of compound (7) with tPL135-136°C.

Example H5: Obtain 2-(2,6-diethyl-4-were)tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione

1.39 g tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione and $ 2.68 g of tert-butyl sodium was dissolved in 20 ml of dimethylformamide at 20°and mixed with 3,21 g of 2,6-diethyl-4-metallobeta, as well as of 0.82 g of PC1(TTF)2Cl2. The mixture is PE is amerivault for 2.5 h at 125° C. After cooling to room temperature, mixed with 200 ml of acetic ether and 200 ml of simple ether and the reaction mixture was subjected to vacuum filtration. The filter cake is mixed with 100 ml of water and the same amount of methylene chloride and acidified with hydrochloric acid. The organic phase is separated, dried and evaporated. The residue (1.9 g) chromatographic on silica gel (acetic ester/hexane in the ratio 3:1). This way you get 2-(2,6-diethyl-4-were)tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione in the form of beige crystals with tPL174-175°C.

Example N6: Obtain 2-(2,6-diethyl-4-were)tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione

1.39 g tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione and $ 2.68 g of tert-butyl sodium was dissolved in 20 ml of dimethylformamide at 20°and mixed with 2.66 g of 2,6-diethyl-4-methylpropanol, as well as of 0.82 g of Pd (TTF)2Cl2. Next, the mixture is stirred for 2.5 h at 125°C. After cooling to room temperature, mixed with 200 ml of acetic ether and 200 ml of simple ether and the reaction mixture was subjected to vacuum filtration. The filter cake is mixed with 100 ml of water and the same amount of methylene chloride and acidified with hydrochloric acid. The organic phase is separated, dried and evaporated. The residue (1.4 g) chromatographic on silica gel (acetic ester/hexane in the ratio 3:1). This way you get 2-(2,6-diethyl-4-meth is fenil)tetrahydropyrazolo[1,2-.is.]pyridazin-1,3-dione in the form of beige crystals with t PL174-175°C.

In the tables below the melting temperature specified in °C. While Me means methyl group. If for Deputy G1-G10and R4and R5(independently from each other) shows the structural formula, the left-hand side of this formula is the point of connection to the oxygen atom of the heterocycle Q1-Q10. In cases where the substituents R4and R5together form specified as the values of the group, the right side of the molecule is a place of connection with the heterocycle Q1. The other end valences are methyl groups.

In subsequent tables, the abbreviation "LC/MS: M+means positively charged molecular ion is expressed in daltons molecular weight, which in the analysis of the product using the apparatus for the combined analysis method GHUR (liquid chromatography high resolution) and MS (mass spectrometry) were amenable to detection in mass spectrum.

Table 1:

The compounds of formula Ia
No.R1R3R4/R5G1Physical. features
1.201ethylethyl-(CH2)4--NtPL209-211
1.202ethylethyl-(CH2)4-tPL125-127
1.203ethylethyltPL195
1.204ethylethyltPL180
1.205ethylethyl-Na wax-like substance
1.206ethylethylsolid
1.1ethylethylcrystalline substance
1.2ethylethyl-Ncrystalline substance
1.3ethyl/td> ethyl-Nsolid
1.4ethylethyl-Nsolid
1.5ethylethyl-Nsolid
1.6ethylethyltPL153 to 155
1.7ethylethyloil
1.8ethylethyloil
1.9ethylethylsolid
1.10ethylethyl-Nsolid
1.11ethylethyl -Na viscous substance

No.R1R3R4/R5G1Physical. features
1.12ethylethyl-Ha viscous substance
1.13ethylethyl-Ha viscous substance
1.14ethylethyl-Ha viscous substance
1.15ethylethyl-Ha viscous substance
1.16ethylethyla viscous substance
1.17ethylethyl-Ha viscous substance
1.18ethylethyl-Hsolid
1.19ethyl ethyl-Hsolid
1.20ethylethylsolid
1.21ethylethyloil
1.22ethylethyla viscous substance
1.23ethylethyl-Ha viscous substance
1.24ethylethyl-Ha viscous substance
1.25ethylethyla viscous substance
1.26ethylethyl-Ha viscous substance
1.27ethylethyl -Hsolid
1.28ethylethylsolid
1.29ethylethyl-Hcrystalline substance
1.30ethylethyl-Ha wax-like substance
1.31ethylethyla viscous substance
1.32ethylethyla viscous substance
1.33ethylethyl-Hsolid
1.34ethylethyla wax-like substance
1.35ethylethyl-Hamorf the second substance

No.R1R3R4/R5G1Physical. features
1.36ethylethyl-Na wax-like substance
1.37ethylethyloil
1.38ethylethyl-Ncrystalline substance
1.39ethylethyl-Nsolid
1.40ethylethylsolid
1.41ethylethyl-NtPL283
1.42ethylethyl-NtPL227
1.43ethyl ethyltPL122-124
1.44ethylethyl-NtPL148-151
1.45ethylethinyl-NtPL163-166
1.46ethylethinyltPL114-116
1.47ethylethyl-Nsolid
1.48ethylethyl-(CH2)4-
1.49ethylethyl-(CH2)4-
1.50ethylethyl-(CH2)4-
1.51ethylethyl-(CH2)4-
1.52ethylethyl-(CH2)4-
1.53ethylethyl-(CH2)4-
1.54ethylethyl-(CH2)4-
1.55ethylethyl-(CH2)4-
1.56ethylethyl-(CH2)4-
1.57ethylethyl-(CH2)4-
1.58ethylethyl-(CH2)4-
1.59ethylethyl-(CH2)4--CH2-OMe

No.R1R3 R4/R5G1Physical. features
1.60ethylethyl-(CH2)4--CH2-SMe
1.61ethylethyl-(CH2)4-
1.62ethylethyl-(CH2)4-
1.63ethylethyl-(CH2)4-
1.64ethylethyl-(CH2)4-
1.65ethylethyl-(CH2)4-
1.66MeO-ethyl-(CH2)4-tPL143-144°C
1.67ethyl-ethinyl-(CH2)4-
1.68-OCHF 2ethyl-(CH2)4-
1.69-SNOethyl-(CH2)4-
1.70ethyl-(CH2)4-
1.71ethyl-(CH2)4-
1.72MeO-MeO--(CH2)4
1.73MeO-ethyl-(CH2)4--NtPL159-161°
1.74ethyl-ethinyl-(CH2)4--N
1.75-OCHF2ethyl-(CH2)4--N
1.76-SNOethyl-(CH2)4--N
1.77 ethyl-(CH2)4--N
1.78ethyl-(CH2)4--N
1.79MeO-MeO--(CH2)4--N
1.80MeO-ethyl-(CH2)4--CO2With2H5tPL112-113°
1.81ethylethyl-NtPL283°C (Razlog.)
1.82ethylethyl-NtPL140°

No.R1R3R4/R5G1Physical. features
1.83MeO-ethyl-Hsolid
1.84MeO-ethyl a wax-like substance
1.85MeO-ethyl-HtPL177-180°
1.86MeO-ethyl-HtPL208-210°
1.87MeO-ethyltPL102-104°C
1.88ethylethyl-HtPL193-194°C
1.89ethylethyltPL163-165°
1.90ethylethylsolid
1.91ethylethyl-Ha wax-like substance
1.92ethylethyl a wax-like substance
1.93ethylethyl-Ha wax-like substance
1.94ethylethyla wax-like substance
1.95ethylethyla viscous substance
1.96ethylethyl-HtPL200-202°C
1.97ethylethyl-HtPL210-220° (Razlog.)
1.98ethylethyl-Hsolid
1.99ethylethinyl-Ha wax-like substance

No.R1R3R4/R5G1The physical is. features
1.100ethylethinyla wax-like substance
1.101ethylethyla viscous substance
1.102ethylethyl-Na wax-like substance
1.103Onsethyla wax-like substance
1.104ethylethyla wax-like substance
1.105ethylethyla wax-like substance
1.106ethylethyla wax-like substance
1.107ethylethyl a wax-like substance
1.108ethylethyla wax-like substance
1.109ethylethyla wax-like substance
1.110ethylethyla wax-like substance
1.111ethinylethyla wax-like substance
1.112ethinylethyla wax-like substance
1.113ethinylethyla wax-like substance
1.114ethinylethyl a wax-like substance
1.115ethinylethyla wax-like substance
1.116ethylethyl-Na wax-like substance
1.117ethylethyl-Na wax-like substance

td align="left">
No.R1R3R4/R5G1Physical. features
1.118ethylethinyl-Na wax-like substance
1.119ethylethinyl-Na wax-like substance
1.120Onsethyl-NtPL130-136°
1.121Onsethyl -NtPL198-200°C
1.122ethylethyla wax-like substance
1.123ethylOnsa wax-like substance
1.124ethinylethyla wax-like substance
1.125ethinylethyla wax-like substance
1.126ethinylethyla wax-like substance
1.127ethylethyl-N
1.128ethylethyl
1.129Onsethyla wax-like substance (LC/MS: M+=552)
1.130Onsethyla wax-like substance (LC/MS: M+=590)
1.131Onsethyla wax-like substance (LC/MS: M+=535)

No.R1R3R4/R5G1Physical. features
1.132Och3ethyla wax-like substance(LC/MS: M+=546)
1.133Och3ethyla wax-like substance (LC/MS: M+=584)
1.134Och3ethylVoskhod the service agent(LC/MS: M +=550)
1.135Och3ethyla wax-like substance (LC/MS: M+=482)
1.136Och3ethyla wax-like substance (LC/MS: M+=550)
1.137Och3ethyla wax-like substance (LC/MS: M+=568)
1.138Och3ethyla wax-like substance (LC/MS: M+=574)
1.139Och3ethyla wax-like substance (LC/MS: M+=580)
1.140Och3ethyla wax-like substance (LC/MS: M+=552)
1.141Och3ethyl a wax-like substance (LC/MS: M+=550)
1.142Och3ethyla wax-like substance (LC/MS: M+=561)
1.143Och3ethyla wax-like substance (LC/MS: M+=520)
1.144Och3ethyl-S(O)2CH3a wax-like substance (LC/MS: M+=454)

No.R1R3R4/R5G1Physical. features
1.145Och3ethyla wax-like substance (LC/MS+=516)
Number 1,146Och3ethylvoskop is such a substance (LC/MS: M +=584)
1.147Och3ethyla wax-like substance (LC/MS: M+=468)
1.148Och3ethyla wax-like substance (LC/MS: M+=496)
1.149Och3ethyla wax-like substance (LC/MS: M+=552)
1.150Och3ethyla wax-like substance (LC/MS: M+=541)
1.151ethylethyla wax-like substance (LC/MS: M+=582)
1.152ethylethyla wax-like substance (LC/MS: M+=620)
1.153ethylethyl a wax-like substance (LC/MS: M+=565)
1.154ethylethyla wax-like substance (LC/MS: M+=576)
1.155ethylethyla wax-like substance (LC/MS: M+=614)
1.156ethylethyla wax-like substance (LC/MS: M+=580)

No.R1R3R4/R5G1Physical. features
1.157ethylethyla wax-like substance (LC/MS:M+=512)
1.158ethylethyla wax-like substance (LC/MS: M+=580)
1.159ethylethyla wax-like substance (LC/MS: M+=642)
1.160ethylethyla wax-like substance (LC/MS: M+=598)
1.161ethylethyla wax-like substance (LC/MS: M+=604)
1,162 noticesethylethyla wax-like substance (LC/MS: M+=546)
1.163ethylethyla wax-like substance (LC/MS: M+=582)
1.164ethylethyla wax-like substance (LC/MS: M+=580)
1.165ethylethyl a wax-like substance (LC/MS: M+=591)
1.166ethylethyla wax-like substance (LC/MS: M+=550)
1.167ethylethyl-S(O)2CH3a wax-like substance (LC/MS: M+=484)

No.R1R3R4/R5G1Physical. features
1.168ethylethyla wax-like substance (LC/MS: M+=546)
1.169ethylethyla wax-like substance(LC/MS: M+=614)
1.170ethylethyla wax-like substance (LC/MS:M+=512)
1.171ethylethyl a wax-like substance (LC/MS: M+=498)
1.172ethylethyla wax-like substance (LC/MS: M+=526)
1.173ethylethyla wax-like substance (LC/MS: M+=582)
1.174ethylethyla wax-like substance (LC/MS: M+=571)
1.175ethylethyla wax-like substance (LC/MS: M+=550)
1.176ethylethyla wax-like substance (LC/MS: M+=588)
1.177ethylethyla wax-like substance (LC/MS:M +=533)
1.178ethylethyla wax-like substance (LC/MS: M+=544)

No.R1R3R4/R5G1Physical. features
1.179ethylethyla wax-like substance (LC/MS: M+=582)
1.180ethylethyla wax-like substance (LC/MS: M+=548)
1.181ethylethyla wax-like substance (LC/MS: M+=480)
1.182ethylethyla wax-like substance (LC/MS: M+=548)
1.183ethylethyl a wax-like substance (LC/MS: M+=566)
1.184ethylethyla wax-like substance (LC/MS: M+=572)
1.185ethylethyla wax-like substance(LC/MS: M+=514)
1.186ethylethyla wax-like substance (LC/MS: M+=550)
1.187ethylethyla wax-like substance (LC/MS: M+=548)
1.188ethylethyla wax-like substance(LC/MS: M+=559)
1.189ethylethyla wax-like substance (LC/MS: M+=518)
1.190 ethylethyl-S(O)2CH3a wax-like substance(LC/MS: M+=452)
1.191ethylethyla wax-like substance (LC/MS: M+=514)

No.R1R3R4/R5G1Physical. features
1.192ethylethyla wax-like substance (LC/MS: M+=582)
1.193ethylethyla wax-like substance (LC/MS: M+=480)
1.194ethylethyl a wax-like substance (LC/MS: M+=466)
1.195ethylethyla wax-like substance (LC/MS: M+=494)
1.196ethylethyla wax-like substance (LC/MS: M+=550)
1.197ethylethyla wax-like substance (LC/MS: M+=539)
1.198ethylethyla wax-like substance (LC/MS: M+=572)
1.199Och3Och3-(CH2)4--ntPL180-193°C
1.200ethylethyl-CO2C2H5tPL153-154°C
Table 2:

The compounds of formula Ia
No.R1R3R4R5G1Physical. har-Ki
2.01ethylethylmethyl-Na wax-like substance
2.02ethylethylmethyl-Nsolid
2.03 ethylethylmethyl-Nsolid
2.04ethylethylmethyla wax-like substance
2.05ethylethylmethyla wax-like substance

No.R1R3R4R5G1Physical. har-Ki
2.06ethylethyl-NtPL171-172
2.07ethylethylin capodanno substance
2.08ethylethyl-Namorphous substance
2.09ethylethylamorphous substance
2.10ethylethyl-N
2.11ethylethylmethylmethyl
2.12ethylethylmethylmethylSO2CH3
2.13ethylMeO-methylmethyl
2.14ethylethinylmethylmethyl
2.15ethylethylmethylphenyl
2.16ethylethylmethyl-3-pyridyl
2.17ethylethylmethyl-2-thienyl
2.18ethylethylmethyl-allyl
2.19ethylethylmethyl-crotyl
2.20ethylethylmethyl-4-chlorophenyl
2.21MeO-MeO-methylallyl-N
2.22ethinylethylphenyl-phenyl-N
2.23ethinylethylphenyl-N
2.24ethylethyl methyl--N
2.25ethylethylmethyl--N
2.26ethylethylphenyl-N
2.27ethylethylmethyl--N
2.28ethylethyl-benzilmethyl--N
2.29ethylethylmethyl--N

ethyl ethyl
No.R1R3R4R5G1Physical. har-Ki
2.30ethylethylmethyl--N
2.31ethylmethyl--N
2.32ethylethyl-(CH2)2OHallyl-NtPL180-185° (Razlog.)
Table 3 (3A and 3b):

The compounds of Formula Ib
No.R1R3R6R7R8G2Physical. har-Ki
3.01ethylethyl-Me-Me-Me-NtPL249-254°C
3.02ethylethyl-Me-N-Me-N
3.03ethyl-CH2-CH2-O-CH2-CH2--Me-N
3.04ethinylethyl-CH2-CH2--allyl-N
3.05ethylethyl-CH2-C(Cl)2--Me
3.06ethylethyl-(CH2)2--Me-N
3.07ethylethyl-(CH2)2-CH(CH3)-(CH2)2--Me-N
3.08ethylethyl-(CH2)2- (CH3)2-(CH2)2--Me-N
3.09ethinylethyl-(CH2)4--Me-N
3.10MeO-ethyl-(CH2)2--N-N
3.11MeO-ethyl-(CH2)2--methyl
3.12-C(O)CH3ethyl-(CH2)2-methyl-H
3.13-OCHF2ethyl-(CH2)2-methyl
3.14ethylethyl-(CH2)3- methyl
3.15ethylethyl-(CH2)5--N-HtPL222-224°C

No.R1R3R6R7R8G2Physical. har-Ki
3.16ethylethyl-(CH2)5--NtPL147-149°
3.17ethylethylmethylmethyl-N-NtPL244-246°
3.18ethylethylmethylmethyl-NtPL164-166°C
3.19ethylethyl-(CH2)5--n-C4H9-NtPL170-175°
3.20ethyle is Il -(CH2)5--n-C4H9tPL99-101°
3.21ethylethyl-(CH2)5-With3H6OMe-Nsolid
3.22ethylethylmethylmethylmethyltPL94-101°C
3.23ethylethyl-(CH2)5-methyl-NtPL252-262°C
3.24ethylethyl-(CH2)5-methyltPL127-128°C
3.25ethylethyl-Ncrystallic. substance
3.26ethylethyla wax-like substance
3.27ethylethyl -Ncrystallic. substance

No.R1R3R6R7R8G2Physical. har-Ki
3.28ethylethylcrystallic. substance
3.29ethylethyl-Nsolid
3.30ethylethyl-Nsolid
3.31ethylethyl
3.32ethylethyl-Namorphous substance

Table 3b
No. R1R3R7R6R8G2Fisiche-Ki
3.33ethylethylmethyl-(CH2)4-
3.34ethylethylmethyl-(CH2)3-
3.35ethylethyl-H-N
3.36ethylethyl-H
3.37ethylethyl-H
3.38ethylethyl-N-N
3.39ethylethyl-N
3.40ethylethyl-N-N

No.R1R3R7R6R8G2Physical. har-Ki
3.41ethylethyl-H
3.42ethylethyl-H-N
3.43ethylethyl-H
3.44ethylethyl-H-N
3.45ethylethyl-H
Table 4:

The compounds of formula Ic

No.R1R3R2R31G3Physical har-Ki
4.01ethylethylmethylmethyl-NtPL224-226°C
4.02ethylethylmethylmethyltPL102-104°C
4.03ethylethylmethylethyl-N
4.04ethylethinylmethylmethyl-N
4.05ethylethinylmethylmethyl
4.06ethylmethoxymethylmethyl-NȀ
4.07ethylethyl-(CH2)2--N
4.08ethylethyl-(CH2)2-CH(CH3)-(CH2)2-
4.09ethylethyl-(CH2)2- (CH3)2-(CH2)2-
4.10ethylethyl-(CH2)4--N
4.11ethylethyl-CH2-CH2-O-CH2-CH2-
4.12ethylethylmethylisopropyl-N
4.13ethylethylmethylethyl-N
4.14ethylethylmethyln-butyl4.15ethylethylmethyl-N
4.16ethylethyl-N-N-NtPL176-178°
4.17ethylethyl-N-NtPL80-82°C
4.18Onsethyl-N-N-NtPL169-171°
4.19Onsethyl-N-Noil
Table 5:

The compounds of formula Id

No.R1R3R32R33G4Physical har-Ki
5.01ethyle is Il methylmethyl-NtPL181-183°C
5.02ethylethylmethylmethyloil
5.03ethylethylmethylethyl-N
5.04ethylethinylmethylmethyl-N
5.05ethylethinylmethylmethyl
5.06ethylmethoxymethylmethyl-N
5.07ethyl/td> ethyl-(CH2)2--N
5.08ethylethyl-(CH2)2-CH(CH3)-(CH2)2-
5.09ethylethyl-(CH2)2- (CH3)2-(CH2)2-
5.10ethylethyl-(CH2)4-
5.11ethylethyl-CH2-CH2-O-CH2-CH2-
5.12ethylethylmethylisopropyl-N
5.13ethylethylmethylethyl-N
5.14ethylethylmethyln-butyl
5.15ethylethylmethylN
5.16ethylethylmethylN-Noil
Table 6:

The compounds of formula Ie
No.R1R3R9R10R11R12G5Physical x is R-Ki
6.01ethylethylmethyl-Nmethyl-N
6.02ethylethylmethylmethyl-N-N
6.03ethylethyl-(CH2)2--N-N-N

No.R1R3R9R10R11R12G5Physical har-Ki
6.04ethylethyl-(CH2)4-methyl-N-N
6.05ethylethyl-(CH2 )2-O-(CH2)2--N-n
6.06ethylethyl-Nmethyl-(CH2)4-
6.07ethylethyl-N-O--N
6.08ethylethyl-N-CH2--N
6.09ethylethinyl-N-(CH2)3--N
6.10ethylMeO--N-(CH2)4--N
6.11ethylethinyl-N-(CH2)4--N
Table 7:

The compounds of formula If
No.R1R2R13R14G6Physical characteristics
7.01ethylethylmethylmethyl-N
7.02ethylethylmethyl-N-N
7.03ethylethyl-Nmethyl-N
7.04ethylethylethylmethyl-N
7.05ethylethyl-(CH2)4--N
7.06ethylMeO--(CH2 )4--N
7.07ethylethinyl-(CH2)4-
7.08ethylethinyl-(CH2)3--N

Table 8:

The compounds of formula Ig
No.R1R2R34R35G7Physical characteristics
8.01ethylethylmethylmethyl-N
8.02ethylethylmethyl-N-N
8.03ethylethyl-Nmethyl -N
8.04ethylethylethylmethyl-N
8.05ethylethyl-(CH2)4-
8.06ethylethyl-(CH2)3-
8.07ethylethinylmethylmethyl
8.08ethylmethoxymethylmethyl
Table 9a:

The compounds of formula Ih
No.R1R3 R15G8Physical. har-Ki
9.01ethylethylmethyl-N
9.02ethylmethoxyphenyl-N
9.03ethylethinyl-4-chlorophenyl-N
9.04ethylethylethyl
9.05ethylethyl-OMe
9.06ethylethyl-CF3

No.R1R3 15G8Physical. har-Ki
9.07ethylethylisopropyl
9.08ethylethyln-butyl
9.09ethylethylcyclopropyl
9.10ethylethylphenyl-NtPL208-209°C
9.11ethylethylphenyltPL147-149°C
9.12ethylethyl-4-tert-butylphenyl-N PL222-224°
9.13ethylethyl-4-tert-butylphenylamorphous substance
9.14ethylethyl-4-tolyl-N
9.15ethylethyl-4-tolyl
9.16ethylethyl-3-chloro-4-forfinal-NtPL186-188°C
9.17ethylethyl-3-chloro-4-forfinaltPL109-110°C
Table 10A,

The compounds of formula Ik
No.R1R3 R16YR17R18G9Physical. har-Ki
10.01ethylethylmethylOmethyl-N
10.02ethylethylmethylOmethylmethyl
10.03ethylethylmethylN-CH3methylmethyl
10.04ethylethylmethyl-N
10.05ethylethylIU is Il -CH2-methylmethyl

methyl
No.R1R3R16YR17R18G9Physical. har-Ki
10.06ethylethylmethyl-CH2-methyl-N
10.07ethylethylethyl-CH2--(CH2)2-
10.08ethylethinylmethyl-CH2--Nmethyl
10.09ethylMeO-methyl-CH2-methylmethyl
10.10ethylethylmethylOmethyl-N -N
10.11ethylethylmethylOmethylmethyl-N
10.12ethylethylmethylN-CH3methylmethyl-N
10.13ethylethylmethyl-N-N
10.14ethylethylmethyl-CH2-methylmethyl-N
10.15ethylethylmethyl-CH2-methyl-N-N
10.16ethylethylethyl-CH2--(CH2)2--N
10.17ethylethinylmethyl-CH2--Hmethyl-N
10.18ethylMeO-methyl-CH2-methyl-N

The following table 21 Me means methyl, Et means ethyl, Pr means propyl and Bu means butyl.

Table 21:

The compounds of formula Im
Conn.No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.1EtEtHHHHHO
21.2EtethinylHHHHHO
21.3EtEtMeMeMeMeHO
21.4EtOMeMeMeMeMeHO
21.5EtEtMeHHHH O
21.6ethinylEtMeHHHHO
21.7EtEtHHMeMeHO
21.8OMeEtHHMeMeHO
21.9EtEtMeHMeMeHO
21.10EtethinylMeHMeMeHO

Me
Conn. No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.11EtEtHMeHMeHO
21.12EtOMeHHMeHO
21.13EtEtMeEtHHHO
21.14ethinylEtMeEtHHHO
21.15EtEtHEtHEtHO
21.16OMeEtHEtHEtHO
21.17EtEtHH-(CH2)4-HO
21.18EtethinylHH-(CH2)4-HO
21.19EtEtHHNHSome3O
21.20Et ethinylHHHHSO2MeO
21.21EtEtMeMeMeMeSome3O
21.22EtOMeMeMeMeMeSO2-n-PrO
21.23EtEtMeHHHSome3O
21.24ethinylEtMeHHHSO2-n-BuO
21.25EtEtHHMeMeSome3O
21.26OMeEtHHMeMeSO2C8H17O
21.27EtEtMeHMeMe Some3O
21.28EtethinylMeHMeMeSO2PhO
21.29EtEtHMeHMeSome3O
21.30EtOMeHMeHMeSO2MeO
21.31EtEtMeEtHHSome3O
21.32ethinylEtMeEtHHSome3O
At 21.33EtEtHEtHEtSome3O
21.34OMeEtHEtHEtSome3O
21.35Et EtHH-(CH2)4-Some3O
21.36EtethinylHH-(CH2)4-Some3O
21.37EtEtHHHHHS
21.38EtethinylHHHHHS
21.39EtEtMeMeMeMeHS
21.40EtOMeMeMeMeMeHS
21.41EtEtMeHHHHS
21.42ethinylEtMeHHHHS
21.43EtEtHHMeMeHS
21.44OMeEtHHMeMeHS
21.45EtEtMeHMeMeHS
21.46EtethinylMeHMeMeHS
21.47EtEtHMeHMeHS
21.48EtOMeHMeHMeHS
21.49EtEtMeEtHHHS
21.50ethinylEtMeEtHHHS
21.51EtEtHEtHEtHS
21.52OMeEtHEtHEtHS
21.53EtEtHH-(CH2)4-HS
21.54EtethinylHH-(CH2)4-HS
21.55EtEtHHHHSome3S

Conn.No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.56EtethinylHHHHSO2MeS
21.57EtEtMeMeMeMeSome3S
21.58EtOMeMeMeMeMeSO2-n-PrS
21.59EtEtMeHHHSome3S
21.60ethinylEtMeHHHSO2-n-BuS
21.61EtEtHHMeMeSome3S
21.62OMeEtHHMeMeSO2C8H17S
21.63EtEtMeHMeMeSome3S
21.64Et ethinylMeHMeMeSO2PhS
21.65EtEtHMeHMeSome3S
21.66EtOMeHMeHMeSO2MeS
21.67EtEtMeEtHHSome3S
21.68ethinylEtMeEtHHSome3S
21.69EtEtHEtHEtSome3S
21.70OMeEtHEtHEtSome3S
21.71EtEtHH-(CH2 )4-Some3S
21.72EtethinylHH-(CH2)4-Some3S
21.73EtEtHHHHHHCH(CH3)2
21.74EtEtHHHHHNCH3
21.75EtEtHHHHHNCH2Ph
21.76EtethinylHHHHHNCH3
21.77EtEtMeMeMeMeHNCH(CH3)2
21.78EtOMeMeMeMeMeHNCH3
At 21.79EtEtMeHHHHNCH(CH3)2
21.80ethinylEtMeHHHHNCH3
21.81EtEtHHMeMeHNCH3
21.82OMeEtHHMeMeHNCH(CH3)2
21.83EtEtMeHMeMeHNCH2Ph
21.84EtethinylMeHMeMeHNCH3
At 21.85EtEtHMeHMeHNCH2Ph
21.86EtOMe HMeHMeHNCH3
21.87EtEtMeEtHHHNCH(CH3)2
21.88ethinylEtMeEtHHHNCH3
21.89EtEtHEtHEtHNCH2Ph
21.90OMeEtHEtHEtHNCH(CH3)2
21.91EtEtHH-(CH2)4-HNCH(CH3)2
21.92EtethinylHH-(CH2)4-HNCH3
21.93OMeEtEtMen HHNCH3
21.94EtEtHHHHSome3NCH(CH3)2
21.95EtEtHHHHSO2MeNCH3
21.96EtEtHHHHSome3NCH2Ph

NCH(CH3)2
Conn. No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.97EtethinylHHHHSO2-n-PrNCH3
21.98EtEtMeMeMeMeSome3NCH(CH3)2
21.99EtOMeMeMeMeMeSO2-n-BuNCH3
21.100EtEtMeHHHSome3NCH(CH3)2
21.101ethinylEtMeHHHSO2C8H17NCH3
21.102EtEtHHMeMeSome3NCH3
21.103OMeEtHHMeMeSO2PhNCH(CH3)2
21.104EtEtMeHMeMeSome3NCH2Ph
21.105EtethinylMeHMeMeSO2MeNCH3
21.106EtEtHMeHMeSome3NCH2Ph
21.107EtOMeHMeHMeSome3NCH3
21.108EtEtMeEtHHSome3NCH(CH3)2
21.109ethinylEtMeEtHHSome3NCH3
21.110EtEtHEtHEtSome3NCH2Ph
21.111OMeEtHEtHEtSomesNCH(CH3)2
21.112EtEtHH-(CH2)4-Some3
21.113EtethinylHH-(CH2)4-SO2C8H17NCH3
21.114OMeEtEtMeHHSO2-n-BuNCH3
21.115EtEtH-(CH2)2-HHCH2
21.116EtethinylH-(CH2)2-HHCH2
21.117EtEt-(CH2)2-HHHCH2
21.118EtOMe-(CH2)2-HHHCH2
21.119EtEtHMeMeHHCH2
21.120ethinylEtHMeMeHHCH2
21.121EtEtEtHHHHCH2
21.122OMeEtEtHHHHCH2
21.123EtEtHHMeMeHCH2
21.124EtethinylHHMeMeHCH2
21.125EtEtHOMeHHHCH2
21.126EtOMeHOMeHHHCH2
21.127EtEtH -(CH2)3-HHCH2
21.128ethinylEtH-(CH2)3-HHCH2
21.129EtEtMeHMeMeHCH2
21.130OMeEtMeHMeMeHCH2
21.131EtEtMeOMeHHHCH2
21.132EtethinylMeOMeHHHCH2
21.133EtEtHSMeHHHCH2
21.134EtOMeHSMeHHHCH2
21.135EtEtMeMeMeMeHCH2
21.136ethinylEtMeMeMeMeHCH2
21.137EtEtOHMeMeMeHCH2

Conn.No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.138OMeEtOHMeMeMeHCH2
21.139EtEtMeSMeHHHCH2
21.140EtethinylMeSMeHHHCH2
21.141EtEtEtEtHMeHCH2
21.142EtethinylEtEtHMeHCH2
21.143EtEtMeMeHCH2OMeHCH2
21.144EtOMeMeMeHCH2OMeHCH2
21.145EtethinylMeSMeHOmeHCH2
21.146EtEtMeSMeHOmeHCH2
21.147EtOMeMeSMeHOmeHCH2
21.148EtEtH-(CH2)2-HSome3CHsub> 2
21.149EtethinylH-(CH2)2-HSome3CH2
21.150EtEt-(CH2)2-HHSO2-n-PrCH2
21.151EtOMe-(CH2)2-HHSomeCCH2
21.152EtEtHMeMeHSomeCCH2
21.153ethinylEtHMeMeHSO2MeCH2
21.154EtEtEtHHHSome3CH2
21.155OMeEtEtHHHSO2-n-PrCH2
2.156 EtEtHHMeMeSome3CH2
21.157EtethinylHHMeMeSO2-n-BuCH2
21.158EtEtHOMeHHSome3CH2
21.159EtOMeHOMeHHSO2C8H17CH2
21.160EtEtH-(CH2)3-HSome3CH2
21.161ethinylEtH-(CH2)3-HSome3CH2
21.162EtEtMeHMeMeSO2-n-PrCH2
21.163OMeEtHMeMeSome3CH2
21.164EtEtMeOMeHHSome3CH2
21.165EtethinylMeOMeHHSO2MeCH2
21.166EtEtHSMeHHSome3CH2
21.167EtOMeHSMeHHSO2-n-PrCH2
21.168EtEtMeMeMeMeSome3CH2
21.169ethinylEtMeMeMeMeSO2-n-BuCH2
21.170EtEtOHMeMeMeSome3CH2
21.171OMeEtOHMeMeMeSO2C8H17CH2
21.172EtEtMeSMeHHSome3CH2
21.173EtethinylMeSMeHHSome3CH2
21.174EtEtEtEtHMeSome3CH2
21.175EtethinylEtEtHMeSO2C8H17CH2
21.176EtEtMeMeHCH2OMeSO2-n-PrCH2
21.177EtOMeMeMeHCH2OMeSome3CH2
21.178/td> EtethinylMeSMeHOMeSome3CH2

Conn, No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.179EtEtMeSMeHOMeSO2C8H17CH2
21.180EtOMeMeSMeHOMeSome3CH2
21.181EtEtH-(CH2)2-HHSNSN3
21.182EtethinylH-(CH2)2-HHSNSN3
21.183EtEt-(CH2)2-HHHSEIN 3
21.184EtOMe-(CH2)2-HHHSNSN3
21.185EtEtHMeMeHHSNSN3
21.186ethinylEtHMeMeHHSNSN3
21.187EtEtEtHHHHSNSN3
21.188OMeEtEtHHHHSNSN3
21.189EtEtHHMeMeHSNSN3
21.190EtethinylHHMeMeHSNSN3
21.191EtEtH-(CH2)2- HSome3SNSN3
21.192EtethinylH-(CH2)2-HSome3SNSN3
21.193EtEt-(CH2)2-HHSO2-n-PrSNSN3
21.194EtOMe-(CH2)2-HHSome3SNSN3
21.195EtEtHMeMeHSome3SNSN3
21.196ethinylEtHMeMeHSO2MeSNSN3
21.197EtEtEtHHHSome3SNSN3
21.198OMeEtEtHHHSO2n-Pr SNSN3
21.199EtEtHHMeMeSome3SNSN3
21.200EtethinylHHMeMeSO2-n-BuSNSN3
21.201EtEtH-(CH2)2-HHC(CH3)2
21.202EtethinylH-(CH2)2-HHC(CH3)2
21.203EtEt-(CH2)2-HHHC(CH3)2
21.204EtOMe-(CH2)2-HHHC(CH3)2
21.205EtEtHMeMeHHC(CH3)2
21.206ethinylEtHMeMeHHC(CH3)2
21.207EtEtEtHHHHC(CH3)2
21.208OMeEtEtHHHHC(CH3)2
21.209EtEtH-(CH2)2-HSome3C(CH3)2
21.210EtethinylH-(CH2)2-HSome3C(CH3)2
21.211EtEt-(CH2)2-HHSO2-n-PrC(CH3)2
21.212EtOMe-(CH2)2-HHSome3C(CH3)2
21.213EtEtHMeMeHSome3C(CH3)2
21.214ethinylEtHMeMeHSO2MeC(CH3)2
21.215EtEtEtHHHSome3C(CH3)2
21.216OMeEtEtHHHSO2-n-PrC(CH3)2
21.217EtEtMeMeMeMeHCHCO2IU
21.218EtEtHHHHHCHCO2IU
21.219EtEtMeMeMeMeSome3CHCO2IU

Conn. No.R1R3R55R137R138R139G10Y2Physical. har-Ki
21.220EtEtNNNNSome3CHCO2IU
21.221EtOMe-(CH2)2-NNNCHCO2IU
21.222EtOMe-(CH2)2-NNSome3CHCO2IU

Biological examples

Comparative experience

In this experiment investigated herbicide action of the following compounds: compound No. 1.02 according to the invention

and connections And

Example B1: Herbicide action before emergence of the plants (preschedule action)

One - and dicotyledonous weed plants are sown in plastic pots with regulatory greenhouse-greenhouse soil mixtures. Immediately after sowing spend processing the tested compounds, the aqueous suspension (obtained from a 25%wettable powder (example F3, b)) or in the form of an emulsion (obtained from a 25%mulgirigala concentrate (example F1, C)) (500 l of water/ha). At this rate of application of active ingredient 500 g/ha After that experienced the plants grown in the greenhouse under optimal conditions. Herbicide action evaluated 3 weeks after treatment for the whole scale (1 corresponds to the full damage, and 9 corresponds to no action). Scores from 1 to 4 (especially 1 to 3) indicate herbicide action from good to very good.

Pilot plants: Alopecurus (Alo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra), see table. B1.

Table B1:

Preschedule action
Preschedule action when the rate of application of active ingredient 500 g/ha
Conn. No.AloAveLolSetPanSorDigEchBra
Connection241214453
1.021111114 11

Example B2: Herbicide action after emergence of the plants (post-harvest action)

One - and dicotyledonous weed plants grown in greenhouse conditions in plastic pots with regulatory greenhouse-greenhouse soil mixtures. Processing pilot plant test compounds is performed on stage 3-6 leaves. The test compounds used in the form of an aqueous suspension (obtained from a 25%wettable powder (example F3, b)) or in the form of an emulsion (obtained from a 25%mulgirigala concentrate (example F1, C)) (500 l of water/ha) when the rate of application of active ingredient 500 g/ha Herbicide action evaluated 3 weeks after treatment for the whole scale (1 corresponds to the full damage, and 9 corresponds to no action). Scores from 1 to 4 (especially 1 to 3) indicate herbicide action from good to very good.

Pilot plants: Alopecurus (Alo), Avena (Ave), Lolium (Lol), Setaria (Set), Panicum (Pan), Sorghum (Sor), Digitaria (Dig), Echinocloa (Ech) and Brachiaria (Bra), see table. B2.

Table B2:

Post-harvest action
Post-harvest action when the rate of application of active ingredient 250 g/ha
Conn.No.AloAveLolSet PanSorDigEchBra
Connection332213212
1.02111111211

A comparison of herbicide activity of compound a and compound No. 1.02 according to the invention allows to conclude that the compound No. 1.02 has unexpectedly significantly higher herbicide effect on all experienced vascular plants, although this connection is different from the connection And only the fact that he has two ethyl groups are replaced by methyl groups.

Example B3: Herbicide action of the compounds according to the invention before emergence of the plants (preschedule action)

One - and dicotyledonous weed plants are sown in plastic pots with regulatory greenhouse-greenhouse soil mixtures. Immediately after sowing spend processing the test compounds in the form of an aqueous suspension (obtained from a 25%wettable powder (example F3, b)) or in the form of an emulsion (obtained from a 25%mulgirigala concentrate (example F1, C)) (500 l of water/ha). At this consumption rate of the active substance SOS which defaults to 500 g/ha After this pilot plants grown in the greenhouse under optimal conditions. Herbicide action evaluated 3 weeks after treatment for the whole scale (1 corresponds to the full damage, and 9 corresponds to no action). Scores from 1 to 4 (especially 1 to 3) indicate herbicide action from good to very good.

Pilot plants: Avena (Ave), Lolium (Lol), Setaria (Set), see table. B3.

Table B3:

Preschedule action (as oil additives use MERGE®at a concentration of 0.7 wt.% in terms of the total weight of the working solution)
Conn. No.Experienced plant
AveLolSet
1.01111
1.02111
1.31112
1.35111

The same results were obtained with the application of the compounds of formula I in the form of the compositions of examples F2 and F4-F8.

Example B4: Herbicide action of the compounds according to the invention after emergence of the plants (post-harvest action) (describing the experience of the see example B2)

Pilot plants: Avena (Ave), Lolium (Lol), Setaria (Set). Obtained in this example the results are presented below in table B4.

Table B4:

Post-harvest action (as oil additives use MERGE®at a concentration of 0.7 wt.% in terms of the total weight of the working solution)
Conn. No.Experienced plant
AveLolSet
1.01111
1.02111
1.04111
1.05131
1.07111
1.08111
1.10111
1.11111
1.14122
1.15121
1.17112
1.19111
1.21111
1.23111
1.26121
1.27112
1.30111
1.31111
1.35111
1.37111
1.39111
1.40112
1.43122

The same results were obtained with the application of the compounds of formula I in the form of the compositions of examples F2 and F4-F8.

1. Phenylsilane heterocyclic 1,3-ketoenol formula I

in which

R1and R3independently from each other mean ethyl or C1-C2alkoxygroup,

Q means a group

where

R4and R5together with the atoms to which they are attached, form a 5-7 membered cycle which optionally contains anilinophenol, asteasu is from 2-6 carbon atoms alkylenes chain, which in turn can contain two heteroatoms selected from oxygen, while this cycle may be substituted with halogen, hydroxy-group,

C1-C6alkoxygroup, C1-C6alkoxy-C1-C6alkoksigruppami, C1-C4alkylcarboxylic, hydroxy-C1-C4-alkoxygroup, hydroxycarbonyl-C1-C2alkoxygroup, methoxycarbonyl-C1-C2alkoxygroup, methoxyimino, methoxyethoxyethoxy,

R6, R7means C1-C10alkyl,

R8means hydrogen,

G1and G2independently of one another denote hydrogen, -C(X1)-R20;

where

X1means oxygen, and

R20means C1-C10alkyl,

and agronomically acceptable salts and isomers of these compounds.

2. Method of producing compounds of the formula I according to claim 1, characterized in that the compound of formula XXX

in which Q represents the Q1, Q2while their deputies with the exception of G1, G2have the above values, and G1and G2mean hydrogen, is subjected to the interaction in the presence of an inert solvent, a base and a palladium catalyst at a temperature of from 30 to 250&#HWS with the compound of the formula XXXI

in which R1and R3are indicated for the formula I, the values a, Hal denotes chlorine, bromine or iodine.

3. Herbicide agent, characterized in that it comprises inert carrier herbicide effective amount of compounds of formula I.

4. A way of combating the growth of unwanted vegetation, characterized in that the plant or place of their growth process herbicide effective amount of the active substance of the formula I or containing this active substance tools.

5. The tool according to claim 3, characterized in that it contains adjuvants that are added to the tank with the preparation for spraying.



 

Same patents:

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new nitrogen-containing aromatic derivatives of the general formula:

wherein Ag represents (1) group of the formula:

; (2) group represented by the formula:

or ; (3) group represented by the formula:

; Xg represents -O-, -S-, C1-6-alkylene group or -N(Rg3)- (wherein Rg3 represents hydrogen atom); Yg represents optionally substituted C6-14-aryl group, optionally substituted 5-14-membered heterocyclic group including at least one heteroatom, such as nitrogen atom or sulfur atom, optionally substituted C1-8-alkyl group; Tg1 means (1) group represented by the following general formula:

; (2) group represented by the following general formula: . Other radical values are given in cl. 1 of the invention claim. Also, invention relates to a medicinal agent, pharmaceutical composition, angiogenesis inhibitor, method for treatment based on these compounds and to using these compounds. Invention provides preparing new compounds and medicinal agents based on thereof in aims for prophylaxis or treatment of diseases wherein inhibition of angiogenesis is effective.

EFFECT: improved treatment method, valuable medicinal properties of compounds and agents.

40 cl, 51 tbl, 741 ex

FIELD: organic chemistry, peptides, medicine, pharmacy.

SUBSTANCE: invention relates to peptide derivatives named as memnopeptides that are used as an active component for manufacturing a medicinal preparation used in treatment of bacterial infection. Invention proposes compound of the formula (I): wherein radicals R1, R2, R3, R4, R5, R6, R7, R8 and (A)n have corresponding values, or its salt. Compounds of the formula (I) are prepared by culturing microorganism Memnoniella echinata FH 2272, DSM 13195 under suitable conditions in the nutrient medium containing at least one source of carbon atoms and at least one source of nitrogen atoms and the process is carrying out until the accumulation of at least one compound of the formula (I) in the nutrient medium followed by isolation of indicated compound. The attained technical result involves the development of a pharmaceutical composition eliciting an antibacterial activity. The development of the preparation provides expanding assortment of agents used in treatment of diseases said above.

EFFECT: improved preparing method, valuable medicinal properties of compounds.

10 cl, 2 tbl, 7 ex

FIELD: pharmaceutical chemistry, medicine.

SUBSTANCE: invention relates to substituted pyridines and pyridazines with angiogenesis inhibition activity of general formula I

(I)1, wherein ring containing A, B, D, E, and L represents phenyl or nitrogen-containing heterocycle; X and Y are various linkage groups; R1 and R2 are identical or different and represent specific substituents or together form linkage ring; ring J represents aryl, pyridyl or cycloalkyl; and G's represent various specific substituents. Also disclosed are pharmaceutical composition containing claimed compounds, as well as method for treating of mammalian with abnormal angiogenesis or treating of increased penetrability using the same.

EFFECT: new pyridine and pyridazine derivatives with angiogenesis inhibition activity.

26 cl, 6 tbl, 114 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of cyclic amide of the formula (I)

or its salt, or hydrate, or solvate wherein X represents (C1-C6)-alkyl, (C1-C6)-alkyl substituted with phenyl, (C2-C6)-alkenyl substituted with phenyl or halogenphenyl, (C2-C6)-alkynyl substituted with phenyl, phenyl that can be substituted with (C1-C6)-alkyl; one or more halogen atom, nitro-group, phenyl, (C1-C6)-alkoxy-group, halogen-(C1-C6)-alkyl, halogen-(C1-C6)-alkoxy-group, phenyl-(C1-C6)-alkyl, (C1-C6)-alkoxyphenyl-(C1-C6)-alkyl, amino-group, optionally substituted with (C1-C6)-alkyl, acetyl, (C1-C6)-alkoxy-group, substituted with phenyl, phenylcarbonyl, furanyl; 1- or 2-naphthyl, monocyclic (C3-C8)-cycloalkyl, amino-group substituted with one or more substitutes taken among phenyl, halogenphenyl, (C1-C6)-alkoxyphenyl, (C1-C6)-alkyl, halogen-(C1-C6)-alkyl, phenyl-(C1-C6)-alkyl; 5- or 6-membered monocyclic heterocyclic group comprising 1 or 2 heteroatoms, such as nitrogen (N), oxygen (O), sulfur (S) atom optionally substituted with halogenphenyl, halogen atom, benzyl, (C1-C6)-alkyl, phenyl; 8-10-membered bicyclic heteroaryl group comprising 1 or 2 heteroatoms taken among N, O and optionally substituted with halogen atom; 8-10-membered polycyclic cycloalkyl group; Q means -CH2-, -CO-, -O-, -S-, -CH(OR7)- or -C(=NR8)- wherein R7 means hydrogen atom (H), (C1-C6)-alkyl; R8 means OH, (C1-C)-alkoxy-group, acylamino-group, (C1-C6)-alkoxycarbonylamino-group, phenyl-(C1-C6)-alkoxy-group; n = 0-5; B represents group or wherein each among R3, R4, R5 and R6 represents independently substitute taken among group consisting of hydrogen atom (H), halogen atom, NO2 (nitro-group), (C1-C6)-alkoxy-group, CN (cyano-group); m = 1 or 2; ring represents 5- or 6-membered aromatic heterocyclic ring comprising one or two heteroatoms taken among O, S, N. Compound of the formula (I) elicit activity inhibiting binding sigma-receptors that allows their using as component of medicinal agent.

EFFECT: valuable medicinal properties of compounds.

21 cl, 2 sch, 4 tbl, 183 ex

The invention relates to new derivatives of 2,3-benzodiazepine of the formula 1

where R1-R4have the meanings specified in the description, has a neuroprotective effect, as well as to methods for their preparation, pharmaceutical compositions and method of treatment of symptoms, followed by all types of acute and chronic neurodegeneration

The invention relates to compounds represented by formulas (I), (II), (III)

The proposed compound of formula M as an intermediate product,

where R denotes the ethyl radical

The invention relates to derivatives of 6-sulfamoylbenzoic-4-carboxylic acid of formula (1), where R1, R2, R3and R4such as defined in the claims

3-piperidine, methods for their preparation and pharmaceutical composition based on them" target="_blank">

The invention relates to tricyclic3-piperidinol General formula (1), where X is O or S, R1means hydrogen, halogen, C1-6alkyl or C1-4alkyloxy, Alk means C1-6alcander, a D such as defined in the claims

The invention relates to the field of organic chemistry, namely to new bicyclic derivative

FIELD: organic chemistry, biochemistry, medicine, pharmacy.

SUBSTANCE: invention relates to new derivatives of pyridopyrimidines of the formula (I): or (II): wherein Z means nitrogen atom (N) or -CH; W means -NR2; X1 means oxygen atom (O), -NR4 (wherein R4 means hydrogen atom or alkyl), sulfur atom (S) or -CR5R6 (wherein R5 and R6 mean hydrogen atom); X2 means oxygen atom (O); Ar1 means unsubstituted or substituted phenyl; R2 means hydrogen atom, alkyl or acyl; R1 means hydrogen atom, alkyl, halide alkyl and others; R3 means alkyl; cycloalkyl and others; R8 and R9 mean hydrogen atom, alkylsulfonyl and others, and to their pharmaceutically acceptable salts, and to intermediate compounds that are used for preparing compounds of the formula (I) and (II). Indicated compounds show inhibitory activity with respect to activity of p38 kinase and can be used in preparing a medicine agent for treatment of p38-mediated disturbances.

EFFECT: improved preparing methods, valuable medicinal properties of compounds and composition.

38 cl, 3 tbl, 116 ex

FIELD: biochemistry, medicine, in particular new bioactive compounds having peptide hormone vasopressin agonistic activity.

SUBSTANCE: disclosed are compounds of general formula 1 or 2 or tautomers, or pharmaceutically acceptable salts thereof, wherein W represents N or C-R4; R1-R4 are independently H, F, Cl, Br, alkyl, O-alkyl, NH2, NH-alkyl, N(alkyl)2, NO2 or R2 and R3 together may form -CH=CH-CH=CH-; G1 represents bicyclic or tricyclic condensed azepine derivatives selected from general formulae 3-8 wherein A1, A4, A7, and A10 are independently CH3, O, and NR5; A2, A3, A9, A11, A12, A14, and A15 are independently CH and N; or A5 represents covalent bond and A6 represents S; or A5 represents N=CN and A6 represents covalent bond; A8 and A12 are independently NH, N-CH3 and S; A16 and A17 both represent CH2 or one of A16 and A17 represents CH2 and the other represents CH(OH), CF2, O, SOa, and NR5; R5 represents H, alkyl, CO-alkyl, and (CH2)bR6; R6 represents phenyl, pyridyl, OH, CO2H; a = 0-2; b = 1-4; Y represents CH or N; Z represents CH=CH or S; and G2 represents group selected from groups of formulae 9-11 wherein Ar represents phenyl, pyridyl, naphthyl, and mono- or polysubstituted phenyl, pyridyl, wherein substituents are selected from F, Cl, Br, alkyl, NO2; D represents covalent bond or NH; E1 and E2 both are H, OMe, F, or one of E1 and E2 represents OH, O-alkyl, OBn, OPh, OAc, F, Cl, Br, N2, NH2, NHBn or NHAc and the other represents H; or E1 and E2 together form =O, -O(CH2)gO- or -S(CN2)gS-; F1 and F2 both represent H or together form =O or =R; L represents OH, O-alkyl, NH2, NH-alkyl, and NR9R10; R7 represents COR8; R8 represents OH, O-alkyl, NH2, NH-alkyl, N(alkyl)2, pyrolidinyl, and piperidinyl; R9 and R10 both are alkyl or together form -(CH2)h-; V represents O, N-CN or S; c = 0 or 1; d = 0 or 1, e = 0 or 1; f = 0-4; g = 2 or 3; h = 3-5, with the proviso, that both d and e are not 0. Also disclosed are pharmaceutical composition having agonistic activity in relate to V2 receptor, method for treatment one or more diseases (e.g., enuresis, nycturia, diabetes insipidus, hemorrhage disorders, urinary incontinence.

EFFECT: new compounds with value biological characteristics.

41 cl, 19 tbl, 193 ex

FIELD: organic chemistry, amino acids, medicine, pharmacy.

SUBSTANCE: invention relates to using derivatives of cysteine for preparing a medicinal agent. The proposed agent is designated for treatment of diseases arising as a result of formation of heterotrimeric protein G, and to new derivatives of cysteine, and pharmaceutical composition based on thereof. Derivatives of cysteine, in particular, involve the following compounds: bis-1,1'-[7-(2-amino-1-oxo-3-thiopropyl)-8-(cyclohexylmethyl)-2-(2-methoxyphenyl)-5,6,7,8-tetrahydroimidazo-[2,2a]-pyrazine]-disulfide and bis-1,1'-[7-(2-amino-1-oxo-3-thiopropyl)-2-91-naphthyl)-8-(2-methylpropyl)-5,6,7,8-tetrahydroimidazo-[1,2a]-pyrazine-7-yl]-disulfide. Invention provides high effectiveness of treatment.

EFFECT: valuable medicinal properties of compounds.

6 cl, 7 dwg, 2 tbl, 7 ex

FIELD: organic chemistry, chemical technology, medicine, pharmacy.

SUBSTANCE: invention describes bicyclic N-acylated imidazo-3-amines or imidazo-5-amines salts of the general formula (I): wherein R1 means tert.-butyl, 1,1,3,3-tetramethylbutyl, (C4-C8)-cycloalkyl, phenyl disubstituted with (C1-C4)-alkyl, -CH2Ra wherein Ra means the group -CO(OR') wherein R' means (C1-C8)-alkyl; R2 means hydrogen atom, the group -CORb wherein Rb means (C1-C8)-alkyl or (C3-C8)-cycloalkyl; R3 means (C1-C8)-alkyl, (C3-C8)-cycloalkyl, phenyl, pyridyl, furfuryl or thiophenyl; A means tri-linked fragment of ring of the formula: wherein R6 and R7 mean hydrogen atom or tetra-linked fragment of ring of the following formulae: wherein R4' means hydrogen atom or benzyloxy-group; R5' means hydrogen atom; R6' means hydrogen atom, (C1-C8)-alkyl or nitro- (NO2)-group; R7' means hydrogen atom, (C1-C8)-alkyl, or R6' and R7' mean in common the following fragment of ring: -CRi=CRj-CH=CH- wherein Ri and Rj mean hydrogen atom; R5'' means hydrogen, chlorine atom or (C1-C8)-alkyl; R6'' means hydrogen atom; R7''n means hydrogen atom, amino- (NH2)-group or (C1-C8)-alkyl; R4''', R6''' and R7''' mean hydrogen atom; R8 means (C1-C8)-alkyl or (C3-C8)-cycloalkyl; X means anion of inorganic or organic acid, or their acid-additive compounds. Also, invention relates to a method for their preparing and a pharmaceutical composition based on thereof. These new compounds show affinity to opiate μ-receptor and can be used, in particular, as analgesic agents.

EFFECT: improved preparing method, valuable medicinal properties of compounds and pharmaceutical compositions.

12 cl, 2 dwg, 32 ex

FIELD: organic chemistry, medicine, hematology.

SUBSTANCE: invention elates to new compounds that inhibit activated blood coagulating factor X (Fxa factor) eliciting the strong anti-coagulating effect. Invention proposes compound of the formula (1): Q1-Q2-C(=C)-N-(R1)-Q3-N(R2)-T1-Q4(1) wherein R1, R2, Q1, Q2, Q4 and T1 have corresponding values, and Q2 represents the group of the formula: wherein R9, R10 and Q5 have corresponding values also, or its salt, solvate or N-oxide. Invention provides the development of a novel compound possessing strong Fxa-inhibiting effect and showing the rapid, significant and stable anti-thrombosis effectin oral administration.

EFFECT: valuable medicinal properties of compounds.

13 cl, 1 tbl, 195 ex

FIELD: organic chemistry, biochemistry, pharmacy.

SUBSTANCE: invention relates to new anellated carbamoyl azaheterocycles of the general formula (1)

or (2) possessing the inhibitory effect on protein kinase activity, a focused library comprising these compounds, and pharmaceutical composition based on thereof. In the general formula (1) or (2) R1 represents hydrogen atom or optionally substituted (C1-C6)-alkyl; R2 and R3 represent independently of one another hydrogen atom, inert substitute, optionally substituted (C1-C6)-alkyl, optionally substituted (C3-C8)-cycloalkyl, optionally substituted phenyl, optionally substituted aryl, optionally substituted heterocyclyl; R4 represents optionally substituted (C1-C6)-alkyl, optionally substituted (C3-C8)-cycloalkyl, optionally substituted phenyl, optionally substituted aryl, optionally substituted heterocyclyl; A and B in common with carbon and nitrogen atoms joined to the form an optionally substituted and optionally condensed azaheterocycle; D and F in common with carbon atoms joined form an optionally substituted and optionally condensed phenyl or aryl, optionally substituted and optionally condensed azaheterocycle. K and L in common with carbon and nitrogen atoms joined to them form an optionally substituted azaheterocycle. Also, invention related to methods for preparing compounds of the general formulae (1) or (2).

EFFECT: improved preparing methods.

10 cl, 2 sch, 25 tbl, 7 ex

FIELD: organic chemistry, biochemistry, pharmacy.

SUBSTANCE: invention relates to a heteroarylamino-substituted derivative of dihydropyrimido[4,5-d]pyrimidinone taken among of compounds order corresponding to the formula (I): wherein a subscript symbol n mans a whole number 1; R1 means (C1-C6)-alkyl (substituted with one or two substitutes taken among group involving hydroxy group, (C1-C6)-alkoxy group and others), piperidinyl-(C0-C4)-alkyl [wherein piperidinyl fragment is monosubstituted optionally with benzyl, carbamoyl, (C1-C4)-alkane sulfonyl, (C1-C6)-alkyl and so on], morpholinyl-(C0-C4)-alkyl, tetrahydropyranyl-(C0-C4)-alkyl, 2-oxoimidazolidinyl-(C0-C4)-alkyl, 2-oxopyrrolidinyl-(C0-C4)-alkyl or 1,1-dioxotetrahydrothienyl-(C0-C4)-alkyl, (C3-C6)-cycloalkyl (monosubstituted with monohydroxy group, (C1-C6)-alkoxy group and so on), 1,4-dioxaspiro[4,5]decane-8-yl, 2,4-dione-1,3-diazaspiro[4,5]decane-8-yl or (3-hydroxymethyl-3-methyl)-1,5-dioxaspiro[5,5]undecane-9-yl; R2 means (C1-C4)-alkyl, halogen atom; R3 means hydrogen atom, (C1-C6)-alkyl (optionally substituted with one or two substitutes taken among group involving (C1-C4)-alkoxy group, pyrrolidinyl, di-(C1-C4-alkyl)-amino-group and so on), phenyl, benzyl or piperidinyl (N-substituted optionally with (C1-C4)-alkyl); R4 means hydrogen atom, and also its individual isomers, racemic and nonracemic mixtures of isomers, prodrugs and its pharmaceutically acceptable salts. Also, invention proposes a pharmaceutical composition possessing inhibitory activity with respect to activity of p38 MAP kinase. The composition comprises a heteroalkylamino-derivative of dihydropyrimido[4,5-d]pyrimidinone of the formula (I), isomer, racemic or nonracemic mixture of isomers or its pharmaceutically acceptable salt in mixture with at least one pharmaceutically acceptable vehicle. Invention provides representing a heteroalkylamino-substituted derivative of dihydropyrimido[4,5-d]pyrimidinone possessing inhibitory activity with respect to activity of p38 MAP kinase.

EFFECT: valuable biochemical properties of compounds and composition.

14 cl, 4 tbl, 90 ex

FIELD: organic chemistry of heterocyclic compounds, biochemistry, pharmacy.

SUBSTANCE: invention describes alkylamino-substituted bicyclic nitrogen-containing heterocycles of the general formula (I):

wherein n = 1; R1 means (C1-C6)-alkyl; R2 means halogen atom; R3 means (C1-C6)-alkoxy-(C1-C6)-alkyl, (C1-C6)-alkylsulfonyl-(C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl, dihydroxy-(C1-C6)-alkyl, N-heterocyclyl-(C1-C6)-alkyl or (C1-C6-alkylene)-C(O)R31 wherein R31 means hydroxy- or (C1-C6)-alkoxy-group, and its pharmaceutically acceptable salts. New compounds are inhibitors of protein kinase p38 and can be used in medicine.

EFFECT: valuable medicinal properties of compounds.

8 cl, 13 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention relates to novel substituted 2-aryl-3-(heteroaryl)imidazo[1,2-a]-pyrimidines of the formula (I):

or to their pharmaceutically acceptable salts wherein: (a) R1 is taken among the group consisting of -NH2, C1-5-alkylamino-, di-C1-5-alkylamino-, phenylmethylamino-group; (b) Y is taken among the group consisting of hydrogen atom (H), halogen atom, piperidine, OR4, SR4, -SO2CH3, NHR4 and NR4R5 wherein R4 and R5 are taken independently among hydrogen atom (H), α-alkylphenyl-C1-5-alkyl, linear or branched alkyl substituted optionally with C3-5-carbocycle, phenyl or substituted phenyl wherein indicated phenyl can be substituted with one or some substituted taken among C1-5-alkoxy-group; (c) R2 represents from one to five members taken independently among the group including hydrogen atom (H), halogen atom, trifluoromethyl; (d) R3 represents hydrogen atom (H), or radicals R3 taken in common form aromatic ring; (e) X represents nitrogen atom (N) or -CH. Also, invention relates to methods for preparing indicated compounds and to a method for treatment based on these compounds. Invention provides preparing novel compounds that can be used in relief states by reducing the level of inflammatory cytokines, for example, the indicated state represents proliferative (rheumatic) arthritis.

EFFECT: valuable medicinal properties of compounds and compositions.

40 cl, 1 tbl, 4 ex

FIELD: organic chemistry, chemical technology, pharmacy.

SUBSTANCE: invention describes derivatives of imidazo-3-ylamine of the general formula (I):

wherein X and Y mean CH or nitrogen atom (N) under condition that X and Y don't mean nitrogen atom (N) simultaneously; R1 means tert.-butyl, (CH2)nCN wherein n means 4, 5 or 6, phenyl substituted optionally with (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C4-C8)-cycloalkyl, 1,1,3,3-tetramethylbutyl or CH2Ra wherein Ra represents hydrogen atom, branched or linear (C1-C8)-alkyl, phenyl substituted optionally with halogen atom, (C1-C4)-alkoxy-group, CO(OR') wherein R' means linear (C1-C4)-alkyl or branched (C3-C5)-alkyl, PO(OR')2 wherein R' means linear (C1-C4)-alkyl or branched (C3-C5)-alkyl; R2 means hydrogen atom, CORb wherein Rb represents branched or linear (C1-C4)-alkyl; R3 means methyl, ethyl, tert.-butyl, (C3-C8)-cycloalkyl, phenyl monosubstituted optionally at position 3, 5 or 6 or optionally multisubstituted at position 4 and additionally at position 2 and/or 3, and/or 5, and/or 6 with halogen atom, hydroxyl group (OH), (C1-C4)-alkyl or (C1-C4)-alkoxy-group, naphthyl, optionally substituted (C1-C4)-alkoxy-group, di-(C1-C4)-alkylamino-group, pyrrole substituted optionally with (C1-C4)-alkyl, benzylsulfonyl, COOCH3, pyridyl substituted optionally with (C1-C4)-alkyl, OH, hydroxy-(C1-C4)-alkyl, furan substituted optionally with (C1-C4)-alkyl, nitro-group (-NO2), halogen-substituted phenyl, CH2COOCH3, COOH, thiophene substituted optionally with halogen atom, (C1-C4)-alkyl, (C1-C4)alkylsulfanyl, -NO2, phenoxy-group, thiophene, alkynylphenyl, unsubstituted anthracene or quinoline substituted optionally with halogen atom under condition that R3 doesn't means cyclohexyl-unsubstituted phenyl or phenyl monosubstituted with carboxylic acid amide at position 3 if R1 means tert.-butyl, n-propyl, n-butyl, 1,1,3,3-tetramethylbutyl, cyclohexyl, monosubstituted phenyl, 2,6-dimethylphenyl or benzyl, and R2 means simultaneously hydrogen atom or -CO-(methyl) and under condition that R2 doesn't mean hydrogen atom if R1 means benzyl simultaneously and R3 means methyl or R1 means simultaneously CH2C(O)-tert.-butyl and R3 means unsubstituted phenyl, in forms of bases or pharmaceutically acceptable salts, and a method for their preparing and a medicinal agent based on thereof. Described compounds possess analgesic activity and can be used in medicine.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

7 cl, 2 tbl, 33 ex

FIELD: organic chemistry, medicine.

SUBSTANCE: invention relates to new compound, 1-(3-aminopropyl)-3-hydroxy-5-(4-fluorophenyl)-4-(4-chlorobenzoyl)-3-pyrroline-2-one hydrochloride of the formula:

that elicits an anti-inflammatory activity that allows its using in medicine. Invention describes a method for its preparing.

EFFECT: valuable medicinal properties of compound.

2 tbl, 1 ex

Up!