Derivatives picolinamides, methods for their preparation, intermediate compounds for obtaining derivatives of picolinamides, method for their preparation and methods of controlling undesirable vegetation

 

(57) Abstract:

The use of the invention as herbicides. The essence of the invention: derivatives of picolinamides formula

< / BR>
where R1-C1-C4-alkyl, possibly substituted with halogen, cyano, methoxy, phenoxy or dimethylaminopropoxy; phenyl, possibly substituted stands, one or two halogen atoms; allyl; propargyl, possibly substituted in the first position one or two WITH1-C4-alkylamino; C3-C5-cycloalkyl; 2,2-dichlorocyclopentane; benzyl; phenethyl; C1-C4-alkoxy; aryloxy; benzyloxy; naphthyl; furfuryl; 3-tert.butyl-isoxazol-5-yl, or trimethylsilyl; R2is hydrogen, C1-C4is alkyl or cyanomethyl, or R1and R2taken together with the nitrogen atom, form morpholino, pyrrolidino, piperidino, which can be replaced by stands, or 3,4-dehydropiperidino, R3is hydrogen, methyl, trifluoromethyl or halogen; R4is hydrogen; n is 1 or 2. Reaction conditions, reagent 1: . Reagent 2: (R3) Reaction conditions: selection of the target product. 7 C. and 2 h.p. f-crystals, 10 PL.

The invention relates to certain new derivative picolinamides, the way they are received, herbicide compositions of the present invention provides compounds of General formula:

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where R1and R2each independently are a hydrogen atom or an alkyl, aryl, alkenyl, quinil, cycloalkyl, cycloalkylation, aralkyl, almariam, hydroxyl, alkoxy, alkenylacyl, alkyloxy, alkylcarboxylic, alkoxycarbonyl, amino, mono - or dialkylamino, alkoxycarbonylmethyl, in which any alkyl, alkanniny, alkynylaryl, cycloalkenyl or aryl fragment optionally substituted by optionally substituted heterocyclic group, killingray, optionally substituted by a halogen atom, dialkylanilines group, trialkylsilyl group or a condensed cyclic structure, or together form alkenylamine chain or optionally substituted alkylenes chain, which is optionally interrupted by an oxygen atom or sulfur or a group-NR-, in which R is a hydrogen atom or alkyl group; R3is a hydrogen or halogen or alkyl, alkoxy, aryl or aryloxy, optionally substituted by one or more identical or different substituents selected among halogen atoms and cyano, hydroxyl and alkoxygroup, or is cyano, carboxyla, alkoxycarbonyl (alkylthio)carbonyl, alkylthio, alkylsulfanyl, alkylsulfonyl, alkyloxyalkyl or algeriaxinhuaalgiers group; R4is a halogen atom or alkyl or haloalkyl; Z is oxygen atom or sulfur, m is 0 to 3 and n is 1 to 4.

If they replaced any of the alkyl, alkenyl, etkinlik, cycloalkyl or aryl fragments in R1and R2may be substituted by identical or different substituents selected among halogen atoms and hydroxyl, cyano, alkyl, alkoxy, alkylthio, alkoxycarbonyl, aryl, aryloxy and mono - or di-alkylamino.

When any of the substituents R1, R2, R3and R4is or contains an alkyl, alkanniny or alkynylaryl Deputy, they can be linear or branched and usually have up to 12, preferably up to 6 carbon atoms. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl and tert.-butyl. When there cycloalkyl replacement group, it usually contains from 3 to 6 carbon atoms in the ring. Aryl group is typically phenyl. Alcanena and Allenova chains usually have 3-6-tier chain. The halogen atom is usually the Teal and triptorelin.

Deputy(and) R3can be anywhere on the provision or combination of provisions pyridylamino rings.

Each substituent R3preferably is hydrogen, chlorine or bromine, or stands, or trifluoromethyl.

Preferably m is 0 and n is 1 2.

Preferably Z is an oxygen atom.

The substituents R1and R2when individually present, may be the same or different. Preferably R1is unsubstituted WITH1-6is an alkyl group WITH1-5is an alkyl group, substituted alkoxy, aryloxy or cyano, or one or more halogen atoms, for example, triptorelin group1-6-an alkoxy group optionally aryl-substituted, WITH2-7-alkenylphenol group2-6-alkenylphenol group2-6-alkenylacyl, unsubstituted aryl group, especially phenyl, substituted aryl group, especially phenyl, substituted by one or more halogen atoms, aranceles group, especially benzyl or fenetylline group, especially trilinos group, cycloalkyl group, especially cyclopropene or cyclopentyloxy group, substituted cycloalkylation monoalkylphenol group, naftilos group or trimethylsilyloxy group, while R2is a hydrogen atom or optionally substituted C1-6is an alkyl group, especially stands, ethyl, n-propylene, ISO-propylene, isobutyl or cyanomethyl, and R3is a hydrogen or halogen atom, or WITH1-6-alkyl or C1-6-haloalkyl.

Especially preferred are compounds in which R1is stands, ethyl, n-propylene, isopropyl, dimethylpropyl, n-bootrom, isobutyl, Deut. -bootrom, tert.-bootrom, methoxy, ethoxy, tert-butoxy, methoxyethyl, cyanomethyl, FORATOM, chloroethyl, triptorelin, allyl, allyloxy, dimethylaminoethyl, propargyl, diethylproprion, diethylproprion, Venetian, jalila, furfuryl, naphthyl, methylpenicillin, trimethylsilyl, tert.-butyl-isoxazolyl, cyclopropyl, cyclopentyl, unsubstituted or monitor, debtor or monochloro-substituted phenyl, benzyl, Formentera, benzyloxy, talila or dichlorsilane cyclopropylmethyl, R2is a hydrogen atom or stands, ethyl, n-propylene, isopropyl, isobutyl or cyanomethyl, and R3is hydrogen, chlorine, bromine or stands, or Tr 4 or 5 links atoms and is, for example, the group -(CH2)4-, -(CH2)5-, -C(CH3)-(CH2)4-, -CH2- - (CH3)-(CH2)3-, -(CH2)2- (CH3)-(CH2)2-,

-(CH2)2O(CH2)2or (CH2)2NR(CH2)2-, in which R is a C1-2-alkyl, typically the stands. When R1and R2together are alkenylamine purpose, usually the circuit consists of 4 or 5 units of atoms and is, for example, a group -(CH2)2-CH=CH-CH2-.

In accordance with the present invention proposed a method of obtaining compounds of General formula I, in which Z is an oxygen atom, which comprises either (a) the interaction of the compounds of General formula:

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with a compound of General formula:

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or (B) the conversion of compounds of General formula:

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in a derivative of General formula:

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which is then injected into the reaction with the amine of General formula other1R2where R1, R2, R3, R4, m and n have the previously indicated meanings. Hal is a halogen atom, X is a hydrogen atom or alkali metal atom, and Z is tsepliaeva group with optional stage of transformation floor the group is any group, which under the reaction conditions will be chipped off from the source material, thus promotora reaction in a particular centre.

Tsepliaeva group Z may be a halogen atom, e.g. a bromine or, especially, chlorine, alkoxygroup, suitably WITH1-4-alkoxy, especially methoxy, or imidazole group.

The transformation of the resulting compounds of General formula I into another compound of General formula I can be such as substitution groups R1and/or R2the other group. For example, when R1and/or R2are a hydrogen atom, they may be replaced by alkyl, usually when interacting with alkyl halide.

l may be a bromine atom or, especially, chlorine atom. X may be a hydrogen atom.

When X is an alkali metal atom, it can be an atom or potassium, especially sodium.

The method is typically carried out in the presence of an inert organic solvent, e.g. dimethylformamide or dimethyl sulfoxide, or an aromatic hydrocarbon, e.g. benzene or toluene, or a halogenated hydrocarbon, e.g. dichloromethane, or simply ether, for example diethyl ether, or complex refereedproceedings at the boiling temperature of the reaction medium, and usually in the presence of a base, such as potassium hydroxide and a copper catalyst, such as odnogolosy copper.

Usually the reaction is carried out using essentially equimolar amounts of the reactants. However, it may be advantageous to use an excess of one of the reagents.

Compounds of General formula I, where Z is a sulfur atom, usually obtained from the interaction of the compounds of General formula I, where Z is an oxygen atom, with paternity phosphorus in standard conditions, for example by heating, suitably at the boiling point under reflux, in the presence of an inert organic solvent, for example benzene, toluene, pyridine or quinoline.

Compounds of the present invention can be isolated or purified by conventional methods, for example, by solvent extraction, evaporation followed by recrystallization or chromatography on silica gel.

The compounds of formula III are either known or can be obtained by traditional methods.

When X is an alkali metal atom, the process according to the method (A) can be carried out to obtain pyridinato alkali metal from the corresponding pyridi is alinost almost equimolar amount of compound (II), usually at elevated temperature, for example at the boiling point under reflux, in the presence of copper catalyst in pyridine in the presence of an aromatic hydrocarbon, such as xylene, as described in the patent application UK N 2050168, or dimethylformamide, or dimethyl sulfoxide.

Compounds of General formula II can be simply obtained by the reaction of an amine of General formula other1R2in which R1and R2have the previously indicated meanings, with a 2-halogen-6-pyridineboronic acid of General formula:

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in which R4, m and Hal have the previously mentioned meanings and Z is tsepliaeva group. Tsepliaeva the group Z defined above.

This reaction is usually carried out in the presence of an inert organic solvent, such as dimethylformamide or acetonitrile, or an aromatic hydrocarbon, e.g. benzene or toluene, or a halogenated hydrocarbon, e.g. dichloromethane, or simply ether, for example diethyl ether, or a complex ester, e.g. ethyl acetate, typically at a temperature in the range from 0 to 100oC. in this way the reaction can be performed using almost equimolar amounts of Reagan is their formula VI can be obtained from the corresponding substituted picolinic acids by standard methods of obtaining, for example, esters using, for example, alcohols and acid catalysts or thionyl chloride, or acid chlorides or bromohydrins acids using, for example, thionyl chloride or thienylboronic, or imidazole derivatives, using, for example, carbonyldiimidazole. Themselves acidic compounds can be obtained by standard methods from chloropicolinic acid or its esters. Chloropicolinic acid or its ester can be obtained according to the methods described, for example, in J. Pharm. Belg. 1980, 35, 1, 5-11.

Substituted amines with other1R2are either known or can be obtained by traditional methods.

The conversion of compounds of General formula IV to the compound of General formula V can be carried out by standard methods, for example, esters using, for example, alcohols and acid catalysts or thionyl chloride, or acid chlorides or bromohydrin acids using, for example, thionyl chloride or thienylboronic, or imidazole derivatives, using, for example, carbonyldiimidazole.

Compounds of General formula IV can be conveniently obtained by hydrolysis of compounds of the General formula:

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in which R3, R4, m and n have th as water or ethylene glycol, using as reagents such acids as hydrochloric, sulfuric and phosphoric acid, or such grounds as potassium hydroxide and sodium hydroxide, at a temperature in the range 0-150oC.

Compounds of General formula VII, which form a further subject of the present invention may be conveniently obtained by the reaction of compounds of General formula:

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in which R4, m and L have the above meanings, with a compound of General formula III, which is also defined above. Conditions such reactions coincide with the conditions of the reaction between the compounds of General formulas II and III, described above.

Compounds of General formula VIII are either known or can be obtained by conventional methods, such as, for example, described Sakamoto t with TCS. Chem. Pharm. Bull. 33 (1985), 565-571, or Bjorn Almanim, Tetrahedron, 41 (1985), 4941-4948.

It was found that compounds of General formula I possess useful herbicide activity. Also it was found that compounds of General formula VII have a certain herbicide activity. Therefore, the present invention also relates to a herbicide composition comprising a compound of formula I or formula VII, as defined above, with at m is at least one carrier.

A carrier in a composition according to the invention is any material with which to formulate the active ingredient to facilitate deposition on the treated places, which may be, for example, plants, seeds or soil, or to facilitate storage, transport or manipulation. The carrier may be solid or liquid, including a material which is normally gaseous but which is compressed with the formation fluid, and can be used any of the carriers normally used in herbicide compositions. Preferably the compositions according to the invention contain 0.5 to 95 wt. the active ingredient.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicates, such as hard-shelled earth, magnesium silicates, such as talc, maggiolini silicates, such as attapulgite and vermiculite, aluminum silicates, for example kaolinites, montmorillonite and mica; synthetic hydrated silicon oxides and synthetic calcium and aluminum silicates; calcium carbonate; calcium sulphate; ammonium sulphate, elements of, for example, carbon and sulfur; natural and synthetic resins, such as coumaric resin, polyvinylchloride.

Suitable liquid carriers include water, alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers, aromatic or analiticheskie hydrocarbons such as benzene, toluene and xylene; petroleum fractions, such as kerosene and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Often suitable mixtures of different liquids.

Agricultural compositions are often formulated and transported in a concentrated form which is then diluted before use. The presence of small amounts of media, which is a surface-active agent, facilitates this process of dilution. Preferably, at least one carrier in a composition according to the invention was surface-active agent. For example, the composition may contain at least two carriers, at least one of which is a surface-active agent.

Surface-active agent may be an emulsifying agent, dispersing agent or wetting agent, it may be nonionic or ionic. Examples of suitable surface-act is nsaty fatty acids or aliphatic amines or amides, containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; complex glycerol esters of fatty acids, esters of fatty acids and sorbitan, sucrose or pentaerythritol; condensates them with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example p-op or p-ochiltree, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, salts of alkaline or alkaline-earth metals, preferably sodium, salts of sulfurous or sulfonic acid esters, containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulfonates, sodium salts from sulphonated castor oil, and sodium alkylarylsulfonate, such as dodecylbenzenesulfonate, and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

Compositions according to the invention can be formulated, for example, in the form of wettable powders, Farrukh Dustov, granules, solutions, mulgirigala concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75 wt. the active ingredient and usually so wt. stabilizer(s) and/or other additives such as penetrants or thickeners. Dusty usually formulated in the form of gustovich concentrates having a composition similar to the composition of a wettable powder but without a dispersant, and it is diluted in the additional solid carrier to obtain a composition usually containing 0.5-10 wt. the active ingredient. Granules are usually prepared to have a size between 10 and 100 BS mesh (1,676-0,152 mm), and they can be manufactured by agglomeration or impregnation. Usually pellets containing 0.5-75 wt. the active ingredient and 0-10 wt. additives such as stabilizers, surface-active agents, modifiers slow allocation and binding agents. The so-called "free flowing powders are composed of relatively small granules having a relatively high concentration of the active ingredient. Mulgirigala concentrates usually contain, in addition to the solvent and, if necessary, co-solvent, 10-50 wt. /volume of active ingredient, 2-20 wt./the amount of emulsifiers and 0-20 wt. /the amount of other additives, such as stabilizers, penetrants and corrosion inhibitors. Suspension concentrates are usually prepared in such a way as to obtain stable, not precipitating fluid productcarousel agent, such as protective colloids and thixotropic agents, 0-10 wt. other additives, such as antifoams, corrosion inhibitors, stabilizers, penetrants and thickeners, and water or an organic liquid in which the active ingredient is practically insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as protivotumanki agents for water.

Aqueous dispersions and emulsions, for example compositions obtained by dilution of a wettable powder or concentrate according to the invention with water, also constitute the subject-matter of the invention. These emulsions can be emulsions water in oil or oil in water, and they can be heavy mainetoday" texture.

The composition of the invention may also contain other active ingredients, for example, compounds with insecticidal or fungicidal properties, or other herbicides.

The present invention further provides the use as herbicides, the compounds of formula I, as defined above, or a composition as defined above, and a method of controlling undesirable grow is to be for example, soil or plants. The dosage used active ingredient may be, for example, in the range of from 0.01 to 10 kg/ha, preferably 0.05 to 4 kg/ha.

The following examples 1-119 illustrate the method And invention examples 1 to 11 illustrate the production of intermediate products of the formula II, while examples 12-119 illustrate the formation of compounds of General formula I.

Example 1. Obtaining N-/4-forfinal/-2-chloro-6-pyridinecarboxamide

Mix 51,2 (0,325 mol) 6-chloropicolinic acid in 90 ml of thionyl chloride and refluxed for 2 hours is Distilled off in vacuum, the excess thionyl chloride and add 250 ml of diethyl ether to the remaining 6 glacialinterglacial. Add with stirring a solution of 37.5 g (0,338 mol) 4-foronline in 100 ml of diethyl ether, maintaining the temperature below 20oC. After the addition the reaction mixture was stirred overnight at room temperature. To the reaction mixture are added water and separate the organic layer. After additional washing with water and drying with anhydrous magnesium sulfate to remove the solvent in vacuo, get the target compound as a pale brown solid (66 g, 82%), so pl. 98oC.

Note the following compounds of General formula other1R2with compounds of General formula IV. The data are given in table. 1.

Elemental analysis data for the intermediate products of General formula II, described above, are presented in table. 2 below.

Example 12. Obtaining N-/4-forfinal/-2-/2'-chloro-4'-pyridyloxy/-6-pyridinecarboxamide

Added 1.3 g (10 mmol) of 2-chloro-4-pyridinol to a solution of 0.56 g of potassium hydroxide in 20 ml of methanol. The solvent is evaporated under vacuum, then add 50 ml of toluene, get anhydrous pyridoxine potassium. The residue is dissolved in 7 ml of anhydrous N,N-dimethylformamide. After adding 2.5 g (10 mmol) N-/4-forfinal/-2-chloro-6-pyridinecarboxamide and 0.1 g odnoklasniki copper mixture is refluxed for 10 hours After cooling, the mixture was poured into 150 ml of water and 100 ml of ethyl acetate. Separate the organic layer and extracted the aqueous phase one or more times 50 ml of ethyl acetate. The combined extracts dried with anhydrous magnesium sulfate and remove the solvent in vacuo. The residue is purified flash chromatography on a column of silica gel using hexane/ethyl acetate (7:3). Get the target compound as a pale yellow solid (1.8 g, 52%), so pl. 102oC.

Examples 13-52.

Analogously to example 12 palermoy III. The data are given in table. 3.

Example 53. Obtaining N-/2,4-differenl/-N-ethyl-2-/3'-chloro-5'-pyridyloxy/-6-pyridinecarboxamide

Added 0.04 g (1.1 mmol) of sodium hydride to a solution of 0.4 g (1.1 mmol) N-/2,4-differenl/-2-/3'-chloro-5'-pyridyloxy/-6-pyridinecarboxamide in 10 ml of anhydrous tetrahydrofuran. After stirring for 30 min was added 0.18 g (1.1 mmol) of ethyliodide carefully, and the mixture is refluxed for 10 hours After cooling, the mixture was poured into 75 ml of water and 100 ml of ethyl acetate. Separate the organic layer and extracted the aqueous phase by adding 100 ml of ethyl acetate. The combined extracts are dried with magnesium sulfate and removed under vacuum of the solvent. The residue is purified flash chromatography on a column of silica gel using hexane/ethyl acetate (7:3). Get the target compound as a white solid (0.16 g, 37%), so pl. 84oC.

Examples 54-119.

Analogously to example 53 obtain compounds of General formula I by converting compounds of the General formula I. the Data are given in table. 4.

The following examples 120-193 illustrate the method (B) of the present invention; examples 120-126 illustrate the production of intermediate compounds of General formula VII, which are novamente General formula IV, and examples 133-193 illustrate the formation of compounds of General formula I.

Example 120. Getting 2-/2'-chloro-4'-pyridyloxy/-pyridine-6-carbonitrile

Add 6 g (46,3 mmol) of 2-chloro-4-oksipiridina to a solution of 2.9 g (50 mmol, 1 EQ. ) of potassium hydroxide in 20 ml of anhydrous methanol at room temperature. The solvent is evaporated under vacuum, then add 100 ml of toluene, get the dry potassium salt. The residue is dissolved in 15 ml of anhydrous N, N-dimethylformamide and added to 6.1 g (45 mmol) of 6-chloropyridin-2-carbonitrile and 0.3 g odnoklasniki copper. The reaction mixture is refluxed with stirring for 3 hours After cooling, the mixture was poured into 100 ml water and the aqueous layer was extracted 3 times with 100 ml of ethyl acetate. The combined extracts dried with anhydrous magnesium sulfate and remove the solvent in vacuo. The residue is purified flash chromatography on a column of silica gel using hexane/ethyl acetate (1: 1). Get the target compound as white crystals (7,3 g, 70%), so pl. 121oC.

Examples 121-126.

Analogously to example 120 is given to the compounds of General formula VII by the interaction of compounds of General formula III with compounds of General formula VIII. Details are given in table. 5.

Prim'-pyridyloxy/-pyridine-6-carbonitrile in 10 ml of concentrated hydrochloric acid and 40 min refluxed. After cooling, add water and the mixture is diluted with 40% aqueous potassium hydroxide solution until, until the mixture becomes transparent. The solution is extracted with ethyl acetate. Then the aqueous layer was acidified with diluted sulfuric acid to precipitate the target compounds in the form of a white solid product (5.6 g, 72%), so pl. 185oC.

Examples 128-132.

Analogously to example 127 is given to the compounds of General formula IV by hydrolysis of compounds of General formula VII. Details are given in table. 6.

Example 133. Obtaining N-/2',2'-dichlorocyclohexyl/-methyl-2-/2'-chloro-4'-pyridyloxy/ -6-pyridinecarboxamide

Refluxed for 30 min 1 g (4 mmol) 2-/2'-chloro-4'-pyridyloxy/-pyridine-6-carboxylic acid (from example 127) in thionyl chloride. The excess thionyl chloride is distilled off in vacuo and to the residue was added 5 ml of acetonitrile. Added under stirring at room temperature a solution of 0.6 g (4.4 mmol) /2',2'-dichlorocyclohexyl/-methylamine and 1.5 ml of triethylamine in 5 ml of acetonitrile, and the mixture is left overnight. Distilled off in vacuum, the solvent, and the residue is dissolved in 25 ml of ethyl acetate. After extraction with dilute aqueous potassium hydroxide organic layer was dried with magnesium sulfate is Zuya hexane/ethyl acetate (1:1). Get the target compound as a pale yellow solid product (0,63 g, 50%), so pl. 106oC.

Examples 134-174

Analogously to example 133 receive other compounds of General formula I by converting compounds of the General formula IV to compounds of General formula V, followed by reaction with compounds of General formula other1R2. Details are given in table. 7.

Example 175. Obtaining N-/2,2,2-triptorelin)-2-/3'-pyridyloxy/-6-pyridinecarboxamide

To a solution of 0.65 g (3 mmol) 2-/3'-pyridyloxy/-pyridine-6-carboxylic acid in 10 ml of anhydrous tetrahydrofuran was added 0.54 g (3.3 mmol) of carbonyldiimidazole and stirred for 30 min, keeping the temperature up to 30oC. was Added 0.4 g (4 mmol) of triptorelin and heated the reaction mixture to 50oC. After 2 h, the solution was poured into 50 ml of water and twice extracted with 100 ml of ethyl acetate. The combined extracts dried over anhydrous magnesium sulfate and remove the solvent in vacuo. The oily residue is heated with hexane to precipitate the target compound as a white solid (0.6 g, 67%), so pl. 92oC.

Examples 176-192.

Analogously to example 175 obtain other compounds of General formula I by converting compounds of the General portali are given in table. 8.

Example 193. Obtaining N-methyl-N-/2,2,2-triptorelin/-2-/2'-chloro-6'-pyridyloxy/ -6-pyridinecarboxamide

Added 0.39 g (1.3 mmol, 80% dispersion in mineral oil) with stirring to a solution of 0.4 g (1.3 mmol) of N-triptorelin-2-/2'-chloro-6'-pyridyloxy/-6-pyridinecarboxamide in 5 ml of anhydrous tetrahydrofuran at room temperature. After 30 min was added 0.2 g (1.4 mmol) under the conditions and the mixture is refluxed for 2 hours, the Reaction mixture was poured into 50 ml water and 50 ml of ethyl acetate. The aqueous layer was extracted twice with ethyl acetate and dried combined extracts with anhydrous magnesium sulfate. Remove the solvent in vacuo, and the residue purified flash chromatography on a column of silica gel using hexane/ethyl acetate (1:1). Get the target compound as a yellow oil (53%).

Elemental analysis data of the compounds of the General formula I, described above, are presented in table. 9 below.

Example 194. Herbicide activity.

To evaluate herbicide activity of the compounds according to the invention were tested using quality range of plants: maize, Zea mays (Mz); rice, Oryza sativa (R); millet batoshevo Echinochloa crusgalli (BG); oat, Avena sativa (O); flax Linum usitatissimum (L); mountains is Educativa and post-harvest processing. Preschedule tests include spraying a liquid formulation of the compounds of the soil, which were previously planted the seeds of the above plants. Post-harvest tests include two types of tests, namely, watering the soil and leaf spray. In a test with irrigation of the soil in which to grow seedlings of plants of the above species, soil watered with liquid formulation containing the compound of the invention, and in tests with leaf spray shoots of plants sprayed with this formulation.

The soil used in the tests was prepared garden loam.

Used in the test formulations were prepared from solutions of test compounds in acetone containing 0.4 wt. condensate of alkylphenol with ethylene oxide, known under the trade name TRITON X-155. The acetone solution was diluted with water and the resulting formulations applied at dose levels corresponding to 5 kg or 1 kg of active material per hectare in the equivalent volume of 600 l/ha in tests on spraying the soil and spraying the leaves, and when the level of the dose equivalent to 10 kg of active material per hectare in a volume equivalent to about 3000 l/ha in trials with irrigation of the soil.

In tests on Elshadai processing use the raw soil with grass plant.

Herbicide action of the tested compounds is assessed visually twelve days after spraying the leaves and soil and thirteen days after watering the soil and is expressed in a scale of 0-9. A score of 0 indicates growth as untreated plants, score 9 points in the loss. An increase of 1 unit on a linear scale corresponds to approximately 10% increase effect.

The results of the tests are presented in table. X below, in which the compounds are identified by reference to an example. The absence of figures in the table indicates a score of zero; an asterisk indicates that the result was not obtained.

1. Derivatives picolinamides General formula I

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where R1C1C4-alkyl, possibly substituted with halogen, cyano, methoxy, phenoxy or dimethylaminopropoxy; phenyl, possibly substituted stands, one or two atoms of halogen; alkyl; propargyl, possibly substituted in the first position by one or two C1C4-alkilani; C3C5-cycloalkyl; 2,2-dichlorocyclopentane; benzyl, phenethyl; C1C4-alkoxy; aryloxy; benzyloxy, naphthyl, furfuryl, 3-tert-butylisoxazole-5-yl, or trimethylsilyl;

R2hydrogen, C1C4-eridano, which may be substituted stands, or 3,4-dehydropiperidino;

R3hydrogen, methyl, trifluoromethyl or halogen;

R4hydrogen;

n is 1 or 2.

2. The method of obtaining compounds of General formula I

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where R1C1C4-alkyl, possibly substituted with halogen, cyano, methoxy, phenoxy or dimethylaminopropoxy, phenyl, possibly substituted stands, one or two atoms of halogen; alkyl; propargyl, possibly substituted in the first position by one or two C1C4-alkilani; C3C5-cycloalkyl; 2,2-dichlorocyclopentane; benzyl; phenethyl; C1C4-alkoxy; aryloxy; benzyloxy; naphthyl; furfuryl; 3-tert-butylisoxazole-5-yl or trimethylsilyl;

R2hydrogen, C1C4is alkyl or cyanomethyl or R1and R2taken together with the nitrogen atom form morpholino; pyrrolidino; piperidino, which can be replaced by stands; or 3,4-dehydropiperidino;

R3hydrogen, methyl, trifluoromethyl or halogen;

R4hydrogen;

n is 1 or 2,

characterized in that interact compounds of General formula II

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with a compound of General formula III

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where R1R4and n have the above znachenii I

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where R1C1C4-alkyl, possibly substituted with halogen, cyano, methoxy, phenoxy or dimethylaminopropoxy; phenyl, possibly substituted stands, one or two halogen atoms; allyl; propargyl, possibly substituted in the first position by one or two C1C4-alkilani; C3C5-cycloalkyl; 2.2 dichlorocyclopentane; benzyl; phenethyl; C1C4-alkoxy; aryloxy; benzyloxy, naphthyl; furfuryl; 3-tert-butylisoxazole-5-yl or trimethylsilyl; R2hydrogen, C1< / BR>
C4-alkyl, or cyanomethyl or R1and R2taken together with the nitrogen atom form morpholino; pyrrolidino; piperidino, which can be replaced by stands, or 3,4-dehydropiperidino,

R3hydrogen, methyl, trifluoromethyl or halogen;

R4hydrogen;

n 1 and 2

characterized in that make the compound of General formula IV

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in a derivative of General formula V

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which is then injected into the reaction with the amine of General formula other1R2where R1R4and n have the above meanings;

L is tsepliaeva group

not necessarily transform the compound obtained of General formula I into another compound of formula I.

4. Link

5. A method of obtaining a connection on p. 4, characterized in that conduct the interaction of compounds of General formula VIII

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where R4and L have the above values,

with a compound of General formula III under item 3.

6. The method of controlling undesirable vegetation by treating the locus of the active ingredient derived picolinamides, characterized in that the quality of the derived picolinamides use the connection I on p. 1 in quantities of 1 to 10 kg/ha.

7. The method of controlling undesirable vegetation by treating the locus of the active ingredient a derivative of pyridine, characterized in that as a derivative of pyridine is used as a compound VII under item 4 in the amount of 1 to 10 kg/ha.

8. The compound of the formula I

< / BR>
where R1C1C4-alkyl, possibly substituted with halogen, cyano, methoxy, phenoxy or dimethylaminopropoxy; phenyl, possibly substituted stands, one or two halogen atoms; allyl; propargyl, possibly substituted in the first position by one or two C1C4-alkilani; C3C5-cycloalkyl; 2,2-dichlorocyclopentane; benzyl; phenethyl; C1C4-alkoxy; aryloxy, benzyloxy, naphthyl; furfuryl; 3-tert-butylisoxazole-5-yl or tste with the nitrogen atom, form morpholino; pyrrolidino; piperidino, which can be replaced by stands, or 3,4-dehydropiperidino;

R3hydrogen, methyl, trifluoromethyl or halogen;

R4hydrogen;

n is 1 or 2,

have a weed-killing activity.

9. Compound of formula VII under item 4, have a weed-killing activity.

 

Same patents:

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Fungicidal tool // 2041627

The invention relates to a derivative of acrylic acid, useful in agriculture (especially as fungicides but also as plant growth regulators, insecticides and nematicides), to the processes of their production, agricultural (especially fungi) compositions containing them and to methods of using them to combat fungi, especially fungal infections of plants, for regulating the growth of plants and to destroy or suppress insect and nematode pests

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

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

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