Derivatives of acrylic acids and their stereoisomers having fungicidal activity

 

(57) Abstract:

Usage: as compounds having fungicidal activity, in agriculture. The inventive product f-crystals and its stereoisomers, where Z is phenyl, optionally substituted by halogen, C1-C4-alkoxy, nitro, cyano, amino, pyrimidine-2-yl, optionally substituted by halogen, pyrimidine-4-yl, optionally substituted by halogen or C1-C4-alkylsulfonyl, pyridine-2-yl, optionally substituted by nitro, cyano, nitrothiazol-2-yl, OCH2CH2O , O, SO2O , CH(OH). Reagent 1: 2-(3-phenoxyphenoxy)-3-cyanopyridine. Reagent 2: alloy skeletal Nickel catalyst of the Raney. Reagent 3: methylsulfonylmethyl sulfide. Reagent 4: methylformate. table 4.

The invention relates to new derivatives of acrylic acid, having fungicidal activity, which can find application in agriculture.

Known compounds of General formula

where R is substituted phenyl, thienyl, benzyl, Z-CR1OH or COOR2< / BR>
R1and R2alkyl having fungicidal activity.

The aim of the invention is to find new compounds with fungicidal activity.

the Oh phenyl, unsubstituted or substituted by halogen WITH1-C4-alkoxy, nitro, cyano, amino; 2-pyrimidinyl, optionally substituted by halogen, 4-pyrimidinyl, optionally substituted by halogen or C1-C4-alkylsulfonyl, pyridine-2-yl, optionally substituted by nitro, cyano or 2-thiazolyl substituted by a nitro-group, X represents a co2CH2OH, OH, SO2O - or-CH(OH) possessing fungicidal activity.

Compounds according to the invention, containing at least one carbon-carbon double bond, sometimes get as mixtures of geometric isomers. However, such mixtures may be separated into individual isomers. This invention covers such isomers and mixtures thereof in all ratios, including the state essentially of (Z) isomer and those that are composed mainly of (E) isomer.

Individual isomers, which are obtained from asymmetrically substituted double bond propenoate group, identified by commonly used terms E and z

The invention is illustrated by the compounds listed in the table.1 and 2, in which methyl-3-methoxypropionate has (EN) configuration.

In table. 3 shows selected indicators on the SS="ptx2">

Chemical shifts are measured in parts 1 million from tetramethylsilane. In all cases used deuterochloroform as solvent. The column, entitled "frequency" refers to the operating frequency of the NMR spectrometer.

Use the following abbreviations:

br wide

s singlet

d doublet

t triplet

q Quartet

m multiplet

The following examples explain the invention. Everywhere in the examples, the term "simple ether refers to diethyl ether. For drying solutions using magnesium sulfate and the solution concentrated under reduced pressure. Reactions, including concentrated under reduced pressure. Reactions involving the formation of intermediate compounds are sensitive to air or moisture, is carried out in nitrogen atmosphere, and the solvent is dried before use, if necessary. In the absence of other indications chromatography carried out on a column with silica gel as stationary phase. Where shown, the data of infrared analysis and NMR are elected; was not trying to bring the list every absorption in all cases. 1H NMR spectra were recorded using solutions of deuterated chloroform in the absence of other the years NMR nuclear magnetic t triplet

resonance m multiplet

IR-infrared wide br

so PL, melting point

P R I m e R 1. This example explains obtain (E)-methyl 2-[2-(3-phenoxyphenoxy)pyrid-3-yl]-4-methoxypropionate (compound 12 in table.1).

A mixture of potassium carbonate (5.53 g 0.04 mol) and 3-phenoxyphenol (15 g, 0.08 mol) in DMF (60 ml) is heated at 80aboutWith stirring 30 min, 2-chloro-3-cyanopyridine (11,08 g, 0.08 mol) and copper in the form of bronze (0.8 g) is added and the resulting mixture heated under reflux for 90 minutes Gaschromatography (GC) analysis showed the formation of a single product (96%). The reaction mixture is cooled, filtered, then poured into water (300 ml) and left to stand in for the weekend. Loose yellow-brown oil is extracted with dichloromethane and dried. Then the dichloromethane solution is filtered and evaporated, giving the crude 2-(2-phenoxyphenoxy)-3-cyanopyridine and 36.2 g, contaminated with DMF, which is used for next step without further purification.

The crude 2-(3-phenoxyphenoxy= -2-cyanopyridine (15 g) is stirred with plavom skeletal Nickel catalyst of the Raney (125 g, 50:50) by boiling under reflux with 75% formic acid (200 ml) 2 hours the Reaction mixture is diluted more, giving an orange oil. Filtration through the filter of silica gel, means for washing of the adsorbent hexameter (1:1), leads to 2-(3-phenoxyphenoxy)-3-formylpyridine 3.03, Infrared analysis: Max. 1685 cm-1. To a stirred solution of aldehyde (3.03 g, 0.01 mol) and methyl tert-sulfanilyl sulfide (1.29 g, 0.01 mol) in dry THF (8 ml) at room temperature add drops of a solution of Triton B (2.5 ml, 40% in methanol). The resulting solution was heated under reflux for 1 h, cooled, then diluted with water. Extraction with dichloromethane followed by drying and evaporation gives a yellow oil, which was dissolved in a methanol solution of hydrogen chloride (100 ml) and left to stand overnight. The methanol is evaporated and the residue treated with saturated sodium bicarbonate solution, then extracted with dichloromethane. The combined organic extracts dried, filtered and evaporated. The remainder chromatographic on silica gel (means for the washing of the adsorbent hexameter 1:1), which gives methyl 2-(3-phenoxyphenoxy)pyrid-3-yl-acetate (1.35 IG) as a pale yellow oil:

1H NMR Delta 3,68 (3H, singlet); 6,74-to 6.88 (3H, multiplet); of 6.96 for 7.12 (4H, multiplet); 7,24-7,40 )3H, multiplet), 7,56-of 7.60 (1H, multiplet); 8 the ID-3-yl-acetate (0.64 g, 0,0019 mol) and methylformate (2,34 ml of 0.038 mol) in DMF (2 ml) is added in drops over 15 min to a stirred suspension washed with petroleum ether sodium hydride (0.18 g, 0,0038 mol/50% suspension in oil) in DMF (10 ml). During the addition the temperature is kept on the level below 10aboutC. the Reaction mixture with intense evolution of gas bubbles becomes yellow in color. The temperature of the solution is allowed to rise to room temperature. Temperature and stirring is continued for 2 hours, the Reaction mixture was poured into water (100 ml), neutralized with diluted hydrochloric acid, then extracted with ether (4 x 25 ml). The combined ether layers washed with water and brine, then dried and evaporated. The obtained yellow oil (0,69 g) dissolved in DMF (10 ml), then stirred with potassium carbonate (0,53 g) 15 min Dimethylsulfate (0.17 ml) were then added in a single portion and stirring is continued for another 4 hours then the reaction mixture was diluted with water (100 ml) and extracted with ether (4 x 25). The combined extracts washed with water and brine, dried, filtered and evaporated, resulting orange oil. The chromatography was carried out on silica gel (means for washing the adsorbent 40:50 petroleum ether ether 1:1) is specified in the header;

1H NMR Delta of 3.64 (3H, singlet); of 3.84 (3H, singlet); 6,72-6,84 (3H, multiplet); 7,00 for 7.12 (4H, multiplet); 7.24 to 7,34 (3H, multiplet); 7,52-of 7.60 (2H, multiplet); 7,56 (1H, singlet), 8,08-to 8.14 (1H, multiplet).

Infrared analysis: Max. 1710, 1640 cm-1.

P R I m m e R 2. This example explains obtain (E)-methyl 2-[2-(3-benzalacetophenone)pyridine-2-yl]-3-methoxy - propenoate (compound 2, table.1).

3-Methoxyphenol (124 g) and anhydrous potassium carbonate (69 g) are heated together with stirring in dry DMF (500 ml) at 80aboutin nitrogen atmosphere. After about 45 min grayish solution is cooled and add 2-chloronicotinate (138,5 g) and copper in the form of bronze (10 g), washed with 100 ml of DMF. The obtained brown reaction mixture is heated to 125-130aboutC. After 2H 30 min, the reaction mixture was cooled and filtered to remove excess copper bronze and undissolved solid material. The resulting solution was added to water (3 l) and left to stand overnight. The precipitate is filtered off, washed with water, then dissolved in ether. The ether solution is dried, filtered and evaporated, giving 2-(3-methoxyphenoxy)-3-cyanopyridine as not quite white solid (203,5 g, 90%).

Melting point: 66-68aboutC.

Infracos) in dry THF (25 ml) at minus 70aboutC in nitrogen atmosphere add drops diisobutylaluminium hydride (27,6 ml, 1.0 mol) at minus 70aboutWith an additional 30 min, then allowed to warmed to room temperature. After 9 h gas chromatographic analysis showed a 30% response. The reaction mixture is cooled to minus 70aboutWith and treated as indicated in the second load diisobutylaluminium (27,6 ml). After 1 h according to gas chromatographic analysis at room temperature, lack of source material. Dilute hydrochloric acid (50%) are added very carefully due to exothermic reaction. The resulting solution was stirred for further 30 min, then separated into layers by means of ether. The aqueous layer was additionally extracted with (x 2) ether. The combined ether layers are dried, filtered and evaporated, resulting in a yellow oil. Chromatography on silica gel (means for the washing of the adsorbent dichloromethane) showed the presence of 2-(3-methoxyphenoxy)-3-pyridinecarboxamide (1.7 g, 33%) as white crystals.

Melting point: 76-78aboutC.

Infrared analysis: Max. 1694 cm-1.

1H NMR Delta, 3,63 (3H, singlet); 6.75 in-6,84 (3A); 7,11-7,15 (1H); 7,33-7,38 (1H); 8,24 compared to 8.26 (1H) 8,35 IS 8.38 (1H), chairein (45 g) make (3 downloads) to 2-(3-methoxyphenoxy)-3-pyridinecarboxamide (34 g, 75%).

To a stirred solution of 2-(3-methoxyphenoxy)-3-pyridine of carboxaldehyde (8,07 g) and methyl methylsulfonylmethyl - sulfide (6,78 ml) in dry THF(20 ml) at room temperature, under nitrogen atmosphere add drops of Triton B (14 ml, 40% solution in methanol). After heating under reflux for 90 min gas chromatographic analysis showed the absence of starting material. The reaction mixture is cooled to room temperature and add dichloromethane (450 ml). After that, the resulting solution was dried, extracted with water (3 x 10 ml). Next, the organic layer dried, filtered and evaporated, giving an orange oil (22,88 g), which is used in subsequent steps without further purification. Orange oil is dissolved in a methanol solution of hydrogen chloride from 300 ml of methanol and 35 ml of acetyl chloride, stirred for 4 h, allowed to stand at room temperature. After 2 days, the solvent is removed and the residue is neutralized with saturated sodium bicarbonate solution. The product is extracted with ethyl acetate. The resulting solution was dried, filtered and evaporated, giving the crude methyl 2-(3-methoxyphenoxy)-3-pyridinyl acetate (13,88 g 90% frequency according to gas chromatography).

Infra the sneeze Delta (9,71 (3H, singlet); 3,76 (2H); 3,95 (3H).

In a separate experiment, 2-(3-methoxyphenoxy)-3-pyridinecarboxamide (93,03 g) turn to methyl 2-(3-methoxyphenoxy)-2-pyridylacetate (28% overall yield 71%).

Methyl 2-(3-methoxyphenoxy)-3-pyridylacetate (27,2 g) is heated at 115aboutWith 47% Hydrobromic acid (249 g) containing hexadecyltrimethylammonium bromide (5.6 g). After 3 hours the solution is cooled and add potassium carbonate to a pH of about 6. The reaction mixture was extracted (5) with ethyl acetate. The organic extracts dried, filtered and evaporated, giving a pale orange solid. Then the solid is treated with a methanol solution of hydrogen chloride, leaving on all night (from methanol (500 ml) and acetyl chloride (50 ml)). The methanol is removed and the residue is dissolved in water. the pH of the solution was added to approximately pH 6 by means of sodium bicarbonate and the solution extracted with ethyl acetate (x 3). The combined organic extracts dried, filtered and evaporated. The residue obtained in the form of a solid orange substance, pererastayut in dichloromethane and filtered through Donny filter of silica gel (means for the washing of the adsorbent ether dichloromethane). Evaporation gives methyl 2-(3-oxii cleanup.

Methyl 2-(3-oxygenase)-3-pyridinyl acetate (0.8 g) and anhydrous potassium carbonate (0.21 g) was stirred together in DMF in a nitrogen atmosphere at 70aboutC. After 20 min, benzyl bromide (1.06 g) is added together with copper to form bronze (catalyst) and the reaction mixture is heated up to 1000about3 hours Analysis showed that the reaction was held at 50% Add a second equivalent of potassium carbonate and benzyl bromide and heating continued at 100aboutWith 2 hours the Reaction mixture is cooled to room temperature, filtered, diluted with water and extracted with ether (X3). The ether extracts are combined dried, filtered and evaporated, giving a brown oil. The chromatography was carried out on silica gel (eluent petroleum ether ether 50:50) to give methyl 2-(3-benzyloxyphenyl)-3-pyridylacetate as a pale yellow solid (0.5 g 46%).

Infrared analysis: Max. 1735 cm-1.

1H NMR (deuterated chloroform), among other Delta 3,70 (3H, singlet); 3,76 (2H, singlet); 5,04 (2H, singlet).

In a separate experiment, obtained additional 0.3 g of product. 2 samples combine to the next level.

A solution containing methyl format (2,85 ml) and methyl 2-(3-benzyloxyphenyl)-2-pyridylacetate (0.8 g) in DMF, to relax the I with petroleum ether) in DMF (10 ml) (liberation of gas bubbles). The temperature is maintained at below 10aboutWith all the added, then up to reach room temperature. After additional 4 h stirring, the reaction mixture is left to stand over the weekend. The reaction mixture was poured into water, in advance podoxranoy dilute hydrochloric acid, then extracted with ether (X3). The combined ether extracts are dried, filtered and evaporated, giving a yellow oil (0,86 g). The oil was dissolved in DMF (10 ml) and treated with potassium carbonate (0.64 g) and dimethylsulfate (0,21 ml) at room temperature. After 4 h stirring gas chromatographic analysis showed the full end of the reaction. Add water (100 ml) and the resulting solution was extracted with ether (3 x 25 ml). The combined ether extracts washed with water, then brine and dried. Filtration and evaporation to give an orange-brown oil. The chromatography was carried out on silica gel (eluent petroleum ether-ether 50:50) causes specified in the title compound as white solid (0.2 g, 22%).

So pl. 119-122aboutC. Mass spectrum m/e 391 (M+).

Infrared analysis: Max. 1705, 1640 cm-1.

1H NMR (deuterated chloroform) Delta 3(1H, singlet); 7,60 to 7.62 (1H, multiplet); 8,08-to 8.12 (1H, multiplet).

P R I m e R 3. This example explains obtain (E)-methyl 2-[2-(3-nitrobenzenesulfonate)phenoxy]pyridine-3 - yl-3-methoxypropionate (compound 9, table.1).

A solution containing methyl 2-(3-oxygenase)-3-pyridylacetate (1 g, obtained as described in example 2) and methylformate (4,68 ml) in DMF (5 ml) is added in drops to a stirred suspension of sodium hydride (0.56 g, 50% dispersion in oil, pre-washed with petroleum ether) in DMF (10 ml). Upon completion of the reaction, the reaction mixture is treated as described previously, which gives the crude methyl 2-[2-(3-oxygenase)pyridine-3-yl]-3-hydroxy - propionate. The product is treated with potassium carbonate (0.31 g) and dimethyl sulfate (0.27 g) in DMF (10 ml) under the conditions described in example 2, which gives after standard processing oil. The chromatography was carried out on silica gel (eluent petroleum ether ether 50: 50 gives (E)-methyl 2-[2-(3-oxygenase)pyridine-3-yl]-3 - methoxypropane in the form of a white solid (0,635 g, 31%).

The melting point of 163-165aboutC, mass spectrum m/e 301 (M+). Infrared spectrum: max 1665, 1633 cm-1.

1H NMR (deuterated chloroform) Delta and 3,68 (3H, singlet); 3,86 (3H, singlet); 6.48 in (1H); 6,54-6,6 (3H); 7.00-7,06 (1H)yl)-3-methoxypropanol] (0,1, obtained as described above) is stirred with 3-nitrobenzenesulfonamide (0,074 ml) and three ethylamine (0,74 ml) in dry dichloromethane (2 ml) at room temperature. After 1 h the reaction mixture is transferred directly to a column of silica gel. Elution with petroleum ether-ether (50:50) gives specified in the title compound as a white spongy solid (0,101 g, 63%).

Melting point: 49-51aboutC. Mass spectrum m/e 486 (M+). Infrared spectrum: 1710, 1638 cm-1.

1H NMR (deuterated chloroform) Delta 3,66 (3H, singlet); of 3.85 (3H, singlet); 6,77-6,83 (2H); 7,00-TO 7.09 (2H); 7,29-7,31 (EN); EUR 7.57 (1H, singlet); 7,60 to 7.62 (1H); 7,71 FOR 7.78 (1H); 8,03-8,08 (1H); parts 1 million.

P R I m e R 4. This example explains obtain (E)-methyl-2-[2-(3- (4-nitrophenoxy)phenoxy)pyridine-3-yl]-3-methoxypropionate (compound 6, table.1).

(E)-Methyl 2-[2-(3-oxygenase)pyridine-3-yl] -3-methoxypropionate (0.3 g, obtained as described in example 1), and potassium carbonate (0,069 g) are heated together with DMF (5 ml) at 70aboutC. After 20 min 4-ftorirovannom (0,141 l ) and copper in the form of bronze (catalyst) is added and the resulting mixture is heated at 130about2 including Gas chromatography indicates the absence of starting material. The reaction stricty dried, filtered and evaporated, giving an orange oil. Chromatography on silica gel causes specified in the title compound as a white crystalline solid (0,266 g, 64%).

Melting point: 102-103aboutC; mass spectrum m/e 422 (M+). Infrared analysis: max 1700, 1625 cm-1.

1H NMR (deuterated chloroform) Delta of 3.64 (3H, singlet); of 3.85 (3H, singlet); 6,80-to 6.88 (2H); 6,94-7,10 (4H); OF 7.36-7,42 (1H); TO 7.59 (1H, singlet); 7,60-to 7.64 (1H); 8,10-TO 8.12 (1H); 8,15 IS 8.22 (2H).

P R I m e R 5. This example explains obtain (E)-methyl-2-[2-(3- (pyrimidine-2-yl-oxy)phenoxy)pyridine-2-yl] -3-methoxypropionate (connected 14, PL.2).

(E)-Methyl 2-[2-(3-oxygenase)pyridine-3-yl]-3-methoxypropionate (0.67 l), obtained as described in example 3 is heated at 80aboutWith potassium carbonate (0,154 g) in DMF (10 ml) under nitrogen atmosphere. After 20 minutes add 2-chloropyrimidine ), 253 g) and copper in the form of bronze (catalyst). The resulting mixture is heated at 130aboutWith under stirring for 2 hours 30 minutes Gas chromatography indicates the end of the reaction. The reaction mixture is cooled, filtered and then poured into water. Next, the aqueous phase is extracted with ether (X3), the combined ether layers are dried, filtered and evaporated, giving a yellowish white tweed solids (0,308, 37% ).

Melting point: 151-153aboutC; mass spectrum m/e 379 (M+). Infrared analysis: max 1695, 1635 cm-1.

1H NMR (deuteromony chloroform) Delta 3,68 (3H, singlet); of 3.85 (3H, singlet); 6,94-7,06 (5H); 7,38-THE 7.43 (1H); EUR 7.57 (1H, singlet); 7,62-7,66 (1H); 8,11-8,15 (1H); 8,53-TO 8.57 (2H); parts 1 million.

P R I m e R 6. This example explains obtain (E)-methyl 2-[2-(3-phenoxyethoxy)pyridine-yl[-3-methoxypropane (compound 1, table.1).

A mixture of 2-chloro-3-pyridinecarboxamide (10.0 g); 3-oxybenzyl alcohol (8,76); anhydrous potassium carbonate (4,76 g); anhydrous potassium carbonate (4,88 g) in DMF (70 ml) is heated under reflux. After 3 h of gas chromatographic analysis showed that all the aldehyde has slashdowns. The reaction mixture is cooled, filtered, then poured into water. The resulting mixture was extracted with ether (X3) and the combined ether layers are washed once with dilute sodium hydroxide solution. Then the ether solution is dried, filtered and evaporated, giving a yellowish-orange oil that crystallized upon standing (9,1 g). To a solution of this product (6,24 g) methylsulfonylmethane (3,38 g) in THF at room temperature under nitrogen atmosphere add drops of Triton B (8 ml, 40% of resiratory and add dichloromethane (300 ml). The resulting solution was extracted with water (X3). The dichloromethane layer is dried, filtered and evaporated, giving a dark orange oil (8.5 g), which are used directly for the next step.

Dark orange oil (8.5 g) of the crude product is dissolved in a methanol solution of hydrogen chloride (from methanol (150 ml) and acetyl chloride (15 ml), stirred for 3 h, then allowed to stand over the weekend. The methanol is removed by evaporation and add saturated aqueous sodium bicarbonate solution. The mixture is extracted with ethyl acetate (X3). The combined organic layers dried, filtered and evaporated, giving a yellow oil. The oil is filtered through a bottom layer of silica gel (eluent dichloromethane, then ether).

Evaporation of solvent gives methyl-2-(3-exomethylene)-3-pyridineacetic in the form of a pale orange oil (Android 4.04 g, 88% purity according to gas chromatography.

Infrared analysis: max 3400, 1737 cm-1.

The product is used for next step without further purification.

A solution of methyl 2-(3-oxygenase)-3-pyridylacetate (0,63 g) and triethylamine (0.45 ml) in dichloromethane (2 ml) is added in drops over 20 min to a stirred solution of methyl chloride (0.02 for the temperature, then leave to stand on the weekend. Gas chromatographic analysis of the aliquot of sample, it indicates the completion of the reaction. The reaction mixture is stirred with brine 30 minutes Then the organic layer is dried, filtered and evaporated, giving methyl-2-(3-chloromethylene)-3-pyridineacetic in the form of a pale yellow oil (0.55 g), which is used directly.

Infrared analysis: Max. 1738 cm-1. Max-spectrum m/e 291 9+).

1H NMR (deuteromony chloroform); among other Delta of 3.69 (3H, singlet); of 3.77 (2H, singlet); 4,60 (2H, singlet).

Phenol (0.16 g) and potassium carbonate (0.12 g) is stirred with DMF (6 ml) under nitrogen atmosphere at room temperature. After 20 minutes add a solution of methyl 2-(3-chloromethylene)-3-pyridylacetate (0.5 g) in DMF and continue mixing. Add copper to form bronze (catalyst) and the reaction mixture is heated at 100aboutWith over 5 hours of gas Chromatographic analysis showed complete reaction. The reaction mixture is cooled, filtered, then poured into water (50 ml). The aqueous mixture is extracted with ether (X3). The combined extracts washed with sodium hydroxide solution. Then the ether solution is dried, filtered and evaporated, giving methyl-2UP>1H NMR (deuteromony chloroform) among others, the Delta of 3.69 (3H, singlet); 3,76 (2H, singlet); 5,07 (2H, singlet) part 1 million. The specified connection contains traces of DMF. When an individual experiences chloromethylene connection (2,73 g), obtained as described above, provides optional 2.00 g of methyl 2-(3-phenoxyethoxy)-3-pyridylacetate.

A solution of methyl 2-(3-phenoxyethoxy)-3-pyridylacetate (3,35 g) and methylformate (6.2 ml) in DMF is added to a suspension of sodium hydride (0.64 g, 60% dispersion in oil, pre-washed with petroleum ether) in DMF (25 ml) under the same conditions as described in the final stage of example 1. Standard treatment leads to crude methyl-[2-(3-phenoxyethoxy)pyridine-3-yl] -3-oxopropyl, that is processed directly by potassium carbonate (1.85 g) and dimethylsulfate (0.63 ml) in DMF (17 ml). Standard processing and chromatography on silica gel (eluent petroleum ether-ether (50:50) are specified in the title compound as a white resin (0,53 g, 1638 cm-1;1NMR are as in table.3).

P R I m e R 7. This example explains obtain (E)-methyl 2-[2-(3-methoxyphenoxy)pyridine-3-yl]-3-methoxy - propionate (compound 4, table.1).

To a cooled ice mix is billaut solution of methyl 2-chloropyrid-3-ylacetic (2 g, 11 mmol) and methylformate (was 12.75 g; 0.22 mol) in DMF (8 ml). The reaction mixture was allowed to warmed to room temperature and stirring is continued until such time as the analysis by the method of thin-layer chromatography shows no residual starting material (about 3 hours). The reaction mixture was poured into water, then acidified with dilute hydrochloric acid. The solution is again extracted with ether and the combined ether extracts are dried, filtered and evaporated. The residue is again dissolved in DMF, and then treated with dimethylsulfate (1,32 g, 10 mmol), and anhydrous potassium carbonate (1.52 g, 11 mmol) at room temperature.

The reaction mixture is stirred for 2 h, diluted with water, and then repeatedly extracted with ether. The combined ether extracts are dried, filtered and evaporated, giving a yellow oil. Chromatography on silica gel (eluent petroleum ether-ether 50:50) to give (E)-methyl 2-(2-chloro-pyrid-3-yl)-3-methoxypropanol in the form of a white similar to the wax substance (0.9 g; 36%). Melting point: 39-40aboutC.

Infrared analysis: Max. 1711, 1638 cm-1.

1H NMR Delta: 3,74 (3H, singlet); the 3.89 (3H, singlet); 7,21-7,26 (1H); 7,55-EUR 7.57 (1H); 7,60 (1H, singlet); 8,32-at 8.36 (1H).

(E)(0,069 g), copper in the form of bronze (catalyst) and copper (I) chloride (catalyst) are heated together at about 170aboutWith 3 h in nitrogen atmosphere. The reaction mixture was cooled, then diluted with a small amount of dichloromethane. The resulting mixture is placed directly on a column of silica gel and chromatographic (eluent petroleum ether-ether 1:1), which gives specified in the title compound as pale brown oil (0,023 g, 6%).

Mass spectrum m/e 407 (M+).1H NMR (deuterated chloroform) are given in table.3.

P R I m e R 8. This example illustrates obtaining (E)-methyl-2-[2-[3-(pyridine-2-yl)oxymethylene]pyridine-3-yl] 3-methoxypropionate (compound 20, PL.2).

A mixture containing 2 g obtained by the method of example 6 methyl 2-(3-chloromethylene)-3-pyridylacetate, 0.64 g of 2-oksipiridina and 1.88 g of silver carbonate in 30 ml of hexane, refluxed 6 hours, the Reaction mixture was partitioned between water and hexane and the aqueous layer was extracted three times with ether. The combined organic extracts dried, filtered and evaporated, getting a brown oil. Chromatography on silicagel (eluent petroleum ether-ether, 1:1) to give methyl 2-[3-pyridin-2-yl)oxymethylene] -3-pyridylacetate (0,, is), 8,03-8,18 (2H, m).

A solution of methyl 2-[3-(pyridin-2-yl)oxymethylene] -3-pyridylacetate (0.56 g) and 1.48 g of methylformate in 5 ml of DMF was added to a suspension of sodium hydride (0.15 g, 50% dispersion in oil, pre-washing with petroleum ether) in DMF under the same conditions as described in the final stage of example 1.

Standard processing gives raw metil-2-[2-[3-(pyridin-yl)oxymethylene] pyridine-3-yl]-3 - oxopropanoic, which directly handle of 0.44 g of potassium carbonate and 0.2 g of dimethylsulfate in 5 ml of DMF 4 hours Standard processing and chromatography on silica gel (eluent ether-petroleum ether, 6:4) gives the target compound as a white oil (0.05 g); IR spectrum: 1711, 1637 cm-1; 1H NMR spectrum (CDCl3) Delta: 3,68 (3H, s), 3,85 (3H, s) 5,38 (2H, s); 6.75 in-6,87 (1H, m), 6,98-7,06 (1H, m), 7,17-of 7.25 (4H, m), 7,37-7,40 (1H, m), 7,58 (1H, s), 7,55-to 7.64 (2H, m), 8.09-8.17 and (2H, m).

P R I m e R 9. This example illustrates obtaining (E)-methyl 2- [2-[3,6-glycinamide-4-yl-okefenokee] pyridine-3-yl] -3 - methoxypropionate (compound 16, table.2).

A mixture containing 0,512 g (E)-methyl 2-(2-(3-oxygenase) MiniDin-3-yl)-3-methoxypropionate obtained by the method of example 3, and to 0.0117 g of anhydrous potassium carbonate in 5 ml of DMF is heated at 80-90aboutC for 1 h in the atmosphere is 5 minutes under stirring to a solution of 4,6-dichloropyrimidine at room temperature. The reaction mixture was stirred overnight and then poured into water and extracted three times with ether. The combined ether extracts washed with diluted sodium hydroxide solution (X3) and water (X3), and then dried, filtered and evaporated, to obtain 0.39 g of a yellow resin. Chromatography on silica gel (eluent ether) gives the target compound in the form of 0.29 g of a yellow resin, which is triturated with ether and petroleum ether, get 0,208 g of the solid product, so pl. 82-84aboutC, mass spectrum m/e 413 (M+);1H-NMR (CDCl3) Delta: 3,70 (3H, C(. of 3.85 (3H, s), 6,91-6,97 (3H, m), 7.03 is-to 7.09 (2H, m), 7,40-7,47 (1H, t), to 7.59 (1H, s), to 7.61-the 7.65 (1H, m), 8,12-of 8.15 (1H, m), at 8.60 (1H, s).

P R I m e R 10. This example illustrates obtaining (E)-methyl-2-[2-[3-(3-cyano% 2 yloxy)phenoxy] pyridine-3 - yl] -3-methoxypropionate (compound 21, PL.2).

A mixture containing 0,301 g (E)-methyl-2-]2-(3-oxygenase) pyridine-3-yl] -3-methoxypropionate obtained by the method of application 3 to 0,069 g of potassium carbonate in 5 ml of DMF, heated in nitrogen atmosphere at 80-90aboutC for 45 minutes Add 0,139 g of 2-chloro-pyridine-3-carbonitrile and a catalytic amount of copper bronze and heat the mixture to 115aboutC. After 75 min, the reaction mixture is cooled, leave overnight, and then poured into the sid of sodium and 3 times with water. The organic layer is dried, filtered and evaporated, to obtain 0.26 g of the resin, which is triturated with ether, to obtain the target compound in the form of a whitish solid product (0,170 g), so pl. 109-112aboutC; IR spectrum 1714, 1632, 2232 cm-1, mass spectrum m/e 403 (M+);1H-NMR (CDCl3) Delta: 3,70 (3H, s), 3,85 (3H, s), 6,95-7,11 (5H, m), 7,38-7,44 (1H, t), to 7.59 (1H, s), 7,0-to 7.64 (1H, m), 7,98 shed 8.01 (1H, m), 8,12-of 8.15 (1H, m), 8,30-of 8.33 (1H, m).

P R I m e R 11. This example illustrates obtaining (E)-methyl-2-[2-[3-(5-nitrothiazol-2-yloxy)phenoxy]pyridine-3 - yl]-3-methoxypropionate (compound 22, table.2).

A mixture containing 0,301 g (E)-methyl 2-(2-3-oxygenase)pyridine-3-yl-3-methoxypropionate obtained by the method of example 3, and was 0.138 g of potassium carbonate in 5 ml of DMF is heated in a nitrogen atmosphere for 1 h at 90aboutC. the Reaction mixture is cooled to room temperature and added in one portion 0,209 g of 2-bromo-5-nitrothiazole. The reaction mixture was stirred at room temperature for 135 min, poured into water and then extracted 3 times with ether. The combined ether extracts washed 3 times with dilute sodium hydroxide solution and 3 times with water, dried, filtered and evaporated, to obtain 0.33 g of an orange resin. Chromatography on silica gel (eluent ether-hexane, 1:1), gives 0.25 g price is: 3,70 (3H, C) of 3.85 (3H, s), 7,05-7,14 (4H, m), 7,43-7,49 (1H, t), 7,60 (1H, s), 7,63-7,66 (1H, d), 8,10-of 8.15 (2H, m).

Examples of compositions suitable for agricultural and horticultural use, which can be prepared from compounds according to the invention.

P R I m e R 12. Emulgirujushchie concentrate produced by blending and mixing the ingredients until full dissolution, the Connection 12 of the table.1 10 Benzyl alcohol 30 Calcium dodecylbenzene - methanesulphonate 5

Nonylphenolethoxylate (13 mol of oxyethylene) 10 Alkyl benzenes 45

P R I m e p 13. The active ingredient is dissolved in methylenechloride and the obtained liquid is sprayed granules of clays "Attapulgite". To obtain a granulated composition then the solvent is allowed to evaporate,

Compound 12 of table.1 5 Granules Attapulgite 95

P R I m e R 14. A composition suitable for use in seed treatment, is produced by grinding and mixing 3 ingredients, Compound 12 of table. 1 50 Mineral oil 2 Kaolin 48

P R I m e R 15. Suitable for pollination powder is produced by grinding and mixing the active ingredients with talcum powder, Compound 12 of table.1 5 Talc 95

P R I m e R 16. A suspension concentrate is produced by grinding in a ball mill ingredients for poucelina 1 Water 49

This recipe can be used for spraying upon dilution with water or by direct application to the seeds.

P R I m e R 17. Formulation wettable powder get joint by mixing and grinding the ingredients until they are thoroughly mixed, Soedinenii table.1 25 Sodium lauryl sulfate 2 Sodium of lignosulfonate 5 Silica gel 25 Kaolin 43

P R I m e R 18. Connections have against a range of fungal diseases of foliage plants. Apply the following techniques.

Plants grown in compost (1 or 2) at the John Innes for use in pots, mini-pots with a diameter of 4 see the Test compound introduced into the formulation or by grinding in a ball mill together with water Dispersion T or in the form of a solution in acetone or in a mixture of acetone with ethanol. The resulting solution is diluted to the required concentration immediately before use. In diseases of the foliage recipes (100 h per million of active ingredient) applied to the foliage by spraying, also applied to the plant roots in the soil. Spray solutions are applied to maximize their hold on the treated surface. Roots irrigate before reaching the end of the e, grain cereals add "Tween 20" before a final concentration 0065% In the majority of test compound applied to the soil (roots) and leaves (by spraying) for 1 or 2 days before plants inoculant the causative agent of the disease. The exception is the test with Erysiphe graminis, which inoculant for 24 h before processing. Pathogenic for foliar pathogens is applied in the form of suspensions of spores by spraying the leaves of test plants. After such spraying is placed in the appropriate environmental conditions for the development of infection. Incubation is carried out before until the disease will not be ready for evaluation. The period from insulinopenia to estimates range from 4 to 40 days, depending on disease and environmental conditions.

Disease register, respectively, the following performance indicators:

4 the absence of disease;

3 from traces to 5% of disease on untreated plants,

2 6-25% of disease on untreated plants, 1 26-59% of disease on untreated plants, 0 60-100% of disease on untreated plants.

The results are shown in table.4.

All connections belong to the category of non-lethal. 1C4-alkoxy, 2-pyridyl, optionally substituted by cyano or nitro, 2-pyrimidinyl, optionally substituted by halogen, 4-pyrimidinyl, optionally substituted by halogen or C1C4-alkylsulfonyl, or 2-thiazolyl substituted by a nitro-group;

X O, OCH2CH2O, SO2O or CH(OH),

having fungicidal activity.

 

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where R1- alkyl-(C1-C4), O-alkyl-(C1-C4), halogen;

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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

FIELD: organic synthesis.

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EFFECT: improved preparing method, valuable properties of compounds.

4 cl, 1 tbl, 7 ex

FIELD: plant protection.

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EFFECT: increased stability of preparation an negative temperatures and upon long-time storage.

2 cl, 2 tbl, 9 ex

FIELD: plant protection.

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2 cl, 3 tbl, 14 ex

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EFFECT: effective controlling of weeds in grain crops.

6 cl, 70 tbl, 3 ex

FIELD: organic chemistry, agriculture, herbicide composition.

SUBSTANCE: invention relates to herbicide composition, containing conventional inert additives and mixture of a) herbicidically effective amount of substance satisfying the formula I [in formula R1 and R3 are the same or different C1-C4-alkyl; R4 and R5 together form groups of formulae: -C-R6(R7)-O-C-R8(R9)-C-R10(R11)-C-R12(R13)-(Z1), -C-R14(R15)-C-R16(R17)-O-C-R18(R19)-C-R20(R21)-(Z2), or -C-R22(R23)-C-R24(R25)-C-R26(R27)-O-C-R28(R29)-(Z3), wherein each R6-R29 is hydrogen; G is hydrogen or -C(X2)-X3-R31; X2 and X3 independently are oxygen; R31 is C1-C10-alkyl]; b) herbicidic synergic amount of at least one herbicide selected from group containing sulfonylureas, phenoxyacetic acids, as well as florsulam, tralcoxidim, klodinafol-propargil, phenoxaprop-P-ethyl, trifluramine, pendimethaline, picolinafen, etc. Composition also may contain safety effective amount of protective agent, such as chloquintocet-mexyl and additive (e.g., mineral oil or C8-C22-fat acid alkyl esters) in amount of 0-2 mass %. Also disclosed is method for selective controlling of weeds and grassy plants in cultural plants by treatment of cultural plants, seeds or seedlings thereof, or vegetation area thereof with claimed composition.

EFFECT: effective composition and method for weed controlling.

5 cl, 11 tbl, 7 ex

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