Derivatives of tetrahydrofuran, the retrieval method and the method of combating fungi

 

(57) Abstract:

Usage: as a fungicide for the prevention and combating fungi. The essence of the invention: derivatives of tetrahydrofuran formula

,

where X1and X2- same or different and denote H, halogen, O-(C1-C4)-alkyl, hydroxy, -S-(C1-C4)-alkyl, hydroxy, -S-(C1-C4)-alkyl, acyl, substituted by halogen, di-(C1-C4-alkyl)amino, (C1-C4)-alkoxyimino, A is phenyl, substituted 2 atoms of halogen, R1-R5- hydrogen. A method of combating fungi by treating the plants or their habitat a compound of formula I in the form of the isomer with the temperature of the coal-seam 96oC or equimolecular mixture of isomers in the amount of 0.11 - 1 kg/ha 3C. and 1 C.p. f-crystals, 3 tables.

The invention relates to a new means of protection of plants. In particular, the invention relates to new derivatives of tetrahydrofuran, to a method for their production and to their use for controlling fungal diseases of plants.

Known from a European patent application N 151084 derivatives of tetrahydrofuran having fungicidal activity.

The challenge is to develop new compounds more vitarana formula I:

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in which

X1and X2the same or different and represent hydrogen, halogen, O-C1-C4-alkyl, hydroxy, -C1-C4-alkyl, acyl, substituted with halogen, di(C1-C4-alkyl)amino, C1-C4-alkoxyimino; A phenyl substituted by two halogen atoms; R1, R2, R3, R4, R5hydrogen;

and their optical isomers, racemates and diastereomers.

The invention relates also to the salts of the compounds according to the invention. Salt forms are used in agriculture and among them we can mention: the hydrate of chlorine, sulfate, oxalate, nitrate or arylsulfonate and additive complexes of these compounds with metal salts, in particular salts of iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum.

The invention relates also to methods of preparing compounds of formula I. Thus, the compounds of formula I, where X2corresponds to the halogen, get in the way, concluding that halogenation formula IIa:

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where A phenyl, substituted 2 atoms of halogen;

R5hydrogen, and

z means a halogen atom;

subjected to interaction with the ORGANOMETALLIC compound of the formula IIb:

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the interaction of the obtained compound of the formula:

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with the unsubstituted triazole in the environment of a mineral or organic base, the compound obtained of the formula:

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where A, R1R5X and Trtake the above values, is treated with a halogen or mixed halogen in an inert solvent and the compound obtained of the formula 11e:

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cyclist in the presence of an organic or mineral base.

The first stage of this method lies in the interaction of compounds of formula IIa with a compound of formula IIb, carried out in a solvent, preferably selected from ethers, for example diethyl ether, tetrahydrofuran; aliphatic, alicyclic or aromatic hydrocarbons, for example hexane, toluene, at temperatures from -50oC to reflux of the given solvent and at a molar ratio of IIa:IIb, preferably comprising 1,1 0,2.

The reaction of compounds of formula IIc with the unsubstituted triazole carried out in the presence of organic or mineral bases, such as pyridine, triethylamine, sodium hydroxide, sodium hydroxide, carbonates and bicarbonates of alkali or alkaline-earth metals, and in an appropriate solvent, such as alcohols, ketones, Amidah, NITRILES, aromatica and at a molar ratio of IIc:triazole, preferably constituting 1,1 0,2, resulting in a receive connection formula IId.

The stage of interaction of the compound (IId) with halogen or mixed halogen exercise adding mole per mole of reagents used and the solvent used, for example, saturated or aromatic, optionally halogenated, hydrocarbons, resulting in a receive connection IIe.

The cyclization of compound IIe carried out preferably at a temperature of ambient air in the environment of such organic or mineral base, which is used in the second step of the method, when a molar ratio of compound IIe: base, preferably at 1.1 0,66. The reaction can be carried out in a proton or an aprotic solvent (water or halogenated aromatic hydrocarbon, dimethyl sulfoxide, amide, for example dimethylformamide).

To obtain the compounds of General formula 1 in which X2means QR6where R6alkyl(C1-C4), and Q denotes an oxygen atom or sulfur, and X1differs from halogen, obtained above compound of formula 1, where X2means halogen, is subjected to the interaction with heteroatomic nucleophile or Quaternary ammonium. The reaction is carried out in an appropriate solvent in the presence of a base and, if necessary, the catalyst phase transition and at the reaction temperature from -30oC to reflux of the applied solvent, at a molar ratio of the reactants, preferably comprising 1,2 0,1.

To obtain compounds of formula 1, when X2corresponds to the hydroxyl group, and X1differs from halogen, it is possible to carry out the reaction in the presence of an inert organic solvent at a temperature of from -30oC to reflux of the solvent, compounds of formula 1, where X2halogen, obtained as described above, with hydropredict, hydroxide, oxide or peroxide alkaline, alkaline-earth metals, or metals, in a molar ratio of the reactants, preferably at 1.1 0,2.

The compounds of formula I, where X2mean S - or O-lower alkyl, and X1differs from halogen, can also be obtained by reacting compounds of formula III:

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where X1differs from halogen, alkylhalogenide when the molar ratio of the reactants, preferably at 1.1 and 0.2, preferably in the presence of an organic or mineral base.

B> means alkyl(C1-C4), and Q denotes oxygen or sulfur, carry out the reaction of the compound of formula IVa or IV:

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in which X1means an oxygen atom or sulfur, linked by a double bond with tetrahydrofuran, with the compound of the formula HQR6when a molar ratio, preferably at 1.1 to 0.2, in the presence of acid catalyst in an appropriate solvent, which may be an alcohol or thiol, or in an inert solvent, such as hydrocarbons or alcohols. If one compound of the formula IVa, the resulting compound then copolymerized with triazole compound.

The compounds of formula IV or IVa, in which X1means an oxygen atom, is obtained by oxidation of compounds of formula III or IIIa:

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where X1means a hydrogen atom, known methods.

The compounds of formula IV or IVa, where X1means a sulfur atom, is obtained by reaction of ionizatsii metafunction, treating the compounds of formula IV or IVa, where X 0, with, for example, H2S or P2S5when the molar ratio of the reactants, preferably at 1.1 to 0.2, in the presence of an inert organic solvent (such as pyridine or hydrocarbons) at a temperature , where R7R8di(C1-C4)-alkyl, produced by the interaction of the compounds of formula I in which H2means halogen, with an amine of the formula H-N-R7R8when the molar ratio of 1.1 and 0.2, optionally in the presence of another organic or mineral bases.

The compounds of formula I, in which X1(or X2) N-R9where R9(C1-C4)-alkoxy, are produced by the interaction of the compounds of formula IV or IVa with an amine of formula R9-NH2or its salt with a molar ratio of preferably 1,1 0,2 in an inert organic solvent. In the case of compounds IVa the compound obtained is subjected to interaction with the triazole compound.

The present invention relates also to the use of compounds of the formula I as fungicides.

Compounds according to the invention can be used both to prevent and to combat fungi, especially basidiomycetes, records of Ascomycetes, delaminate or fungi-deuteromycota especially with rust, powdery mildew, cercosporella, Fusarium, Helminthosporium, Septoria, stem canker of plants and vegetation in General and, in particular, pshenizza to such fungi, as basidiomycetes, records of Ascomycetes, delaminate or fungi-deuteromycota, for example, Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospora beticola, Puccinia striiformis, Erysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria tritici, Venturia inaequalis, Whetzelinia sclerotiorum, Monilia laxa, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Henicillium expansum, Pestalozzia sp. Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma lingam, Ustilago maydis, Verticillium dahliae, Ascochita pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum, Sclerotinia minor, Coryneum cardinale, Rhizoctonia solani.

In addition, they are also actively working on the following fungi: Acrostalagmus koningi, Alternaria, Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuori, Hormodendron cladosporioides, Lentinus degener or tigrinus, Lenzites quercina, Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbum sp. Trametes trabea, Trichderma pseudokoningi, Trichothecium roseum.

Compounds according to the invention is particularly of interest because of their broad-spectrum effects for diseases of cereal powdery mildew, rust, cercosporella, Helminthosporium, Septoria, Fusarium. They are especially active against grey plesnevelae rot of grapes (Botrytis) and Cercospora and therefore they can be used for a variety kulturu, coffee, fruit, pecans, and others.

In addition to the above-mentioned applications of the substances according to the invention find an excellent biocidal activity against many other types of microorganisms, which include, without limiting the scope of the invention, the following fungi:

Pullularia P. pullulans

Chaetomium C. globosum

Aspergillius Aspergillius niger

Coniophora C. puteana

Due to their biocidal activity of the substances according to the invention can effectively combat the microorganisms which multiply creates numerous problems in agriculture and industry. To this end, they are particularly suitable for protecting plants or industrial products, such as wood, leather, paint, paper, ropes, plastics, industrial water supply system.

They are particularly suitable for protection of lignocellulosic products, in particular wood, such as furniture materials, timber or wood exposed to weathering, such as fences, posts in vineyards, railway sleepers.

Compounds according to the invention, used alone or in form of compositions during processing of wood, usually used with organic solvents and can about low, in particular, copper, manganese, cobalt, chromium, zinc and derivatives inorganic or carboxylic acids (heptane, octane, hexahydrobenzene acids); organic complex compounds of tin, 2-mercaptobenzthiazole, insecticides, such as pyrethroids or organochlorines.

In addition, they have excellent selectivity relative to cultures.

They are effectively used in doses of 0.005 to 5 kg/ha, in particular 0,11 1 kg/ha.

The most interesting representative compounds according to the invention is a compound of the formula:

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in the form of an isomer or equimolecular mixture, which is superior fungicidal activity known analogues.

Examples I to VII illustrate the private methods of preparation of compounds according to the invention, as well as connections.

Example 1. Obtaining 1-[4-bromo-2-(2,4-dichlorophenyl)-tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. Connection N 1a, 1b, and 1a + 1b.

Stage a). Obtain 1-chloro-2-(2,4-dichlorophenyl)-4-penten-2-ol.

Prepare magyarkanizsa connection by adding a solution of allylbromide (110 ml) in ethyl ether (700 ml) and tetrahydrofuran (200 ml) with magnesium (110 g) at a temperature of 15 20oC techini">

This organic phase is added at -30oC solution of alpha-trichloro-2,4-acetophenone (175 g) in tetrahydrofuran (250 g), neutralized with acetic acid. Washed with water, dried over sodium sulfate, concentrated, and then distilled in vacuum. Get colorless oil (205 g). Boiling point (310-2mm RT. Art.) 140 142oC.

Stage b). Obtaining 1-[2-(2,4-dichlorophenyl)-2 - hydroxy-4-pentenyl]-1H-1,2,4-triazole.

The mixture obtained in step (a) product (106 g), triazole (55 g) and potassium carbonate (160 g) is heated for 4 hours at 120oC in dimethylformamide (600 ml). The insoluble substance was filtered, washed with dimethylformamide and the reaction mixture was concentrated in vacuo. The residue is dissolved in methylene chloride, washed with water, then concentrated. The product is obtained by crystallization in ethyl acetate after dilution with heptane. Isolate the solid pale pink color with a melting point 101oC.

Stage C). Obtaining compounds N-1a and N-1b.

Obtained in step b), the compound (35 g) in chloroform (200 ml) is treated with bromine at 0oC. After bleaching the solvent is evaporated and the residue is again dissolved in methanol. Then add an aqueous solution of caustic Coda and concentrate. The obtained oil (40 g) consists of a mixture of two diastereoisomers in equal proportion. By chromatography on silica sequentially emit the least polar isomer N 1a: white crystals with a melting point of 83oC, then the most polar isomer N 1b: white crystals with a melting point 94oC. After recrystallization get 1a with a melting point 96oC and 1b with a melting point of 104oC. the Mixture is 50/50 1a and 1b has a melting point of 74oC.

Similarly prepared from the appropriate starting materials the following compounds: 1-(4-bromo-2-(4-chlorophenyl)-tetrahydro-2 - furanyl]-1H-1,2,4-triazole 1c, so pl. 74oC, 1d so pl. 78oC, 1c + 1d so pl. 69oC.

Example II. Obtaining 1-[2-(2,4-dichlorophenyl)-4-hydroxycitrate-2-furylmethyl]-1H-1,2,4-triazole. Connection N 2a and 2b.

10 g of the isomer 1a of example I, which is the least polar isomer dissolved in 30 ml of chlorobenzene is heated under reflux for 48 hours in the presence of 20 g of sodium benzoate in 30 ml of water and 1 g of the catalyst phase transition "ADOGEN 464" methyltrioctylammonium.

After dilution with ether, the organic phase is washed with water and removed in vacuum. Ostavljajut water, extracted with ethyl acetate, washed to a neutral state and purify by chromatography of the resulting crude product after concentration in vacuum. Alcohol 2a isolated in the form of a white powder (2.8 g) with a melting point 193oC.

Producing similar operations with the most polar isomer 1b, obtained in example I, are optically active alcohol 2b, which is formed in the form of a white powder with a melting point of 162oC. the Mixture is 50/50 2a and 2b represents the oil.

Example III. Obtaining 1-[2-(2,4 - dichlorophenyl)-4-ethoxyacrylate-2-furylmethyl]-1H-1,2,4-triazole. Connection N 3a and 3b.

Dissolved in dimethyl sulfoxide (12 ml) alcohol 2a (2.2 g) is treated sequentially 80% solution of sodium hydride (0,42 g), then ethyliodide (1,15 ml). After 15 minutes, the medium is diluted with water and extracted with ethyl acetate. After washing with water, the solvent evaporated and the residue purified by chromatography on silica and receive a colorless oil, which is an isomer 3a, which is crystallized by rubbing in pentane with a melting point 90oC, similarly, from 2b receive isomer 3b in the form of a white powder with a melting point 63oC. the Mixture is 50/50 3a + 3b represents summarized in the following table.

Example IV. Obtaining 1-[1-(2,4-dichlorophenyl)-4-ethylthiomethyl-2-furylmethyl]-1,2,4-triazole. Connection N 7a and 7b.

Dissolved in dimethyl sulfoxide (38 ml) with water (2 ml) and broil 1a (3.8 g) is treated with sodium hydrosulfide (2.8 g) for 2 hours. Then add sodium hydroxide powder (3.3 grams) and ethyliodide (4 ml). After 10 minutes stirring, the medium is diluted with water and extracted with ether. After drying and evaporation receive isomer 7a, representing a yellow oil with a melting point (3,9 g) 88oC.

Producing similar operations 1b, receive 7b in the form of a powder pale yellow color with a melting point 64oC. the Mixture of isomers is an oil.

In a similar manner there were obtained the compounds of formula VIII using the appropriate thiols, are summarized in the following table.

Example V. Obtaining 1-[7-(2,4-dichlorophenyl)-1,4,6-trioxa-Spiro[4,4] 7-nonanimate]-1H-1,2,4-triazole. The Compound N 13.

Stage a). Obtain 1-chloro-2-(2,4-dichlorophenyl)-3,4,5-pentane-Tirol.

Obtained in step a) in example 1, chlorhydrin (91 g) epoxidized in 1,2-dichloroethane (125 ml) in the presence of vanadium acetylacetonate (5 g) and peroxide and tertiary butyl 70% (200 ml) by heating the or of sodium bisulfite and then concentrated. The residue is converted into the triol by heating in water (200 ml) and dioxane (200 ml) in the presence of perchloric acid (5 ml) for 3 hours. After dissolution in water environment is extracted with toluene (300 ml), then concentrated.

Stage b). Getting 2-(2,4-dichlorophenyl)-2-chloromethyl-tetrahydro-4-furanone.

Obtained in step a) the oily residue is heated in toluene (100 ml) and butanol (200 ml) in the presence of paratoluenesulfonyl (0.5 g) separating the formed water. After evaporation of the reaction medium residue chromatographic on silica (eluent ethyl acetate/heptane 40:60) and receive a colorless oil (14.5 g), corresponding to a mixture of diastereoisomeric alcohol, which is a 2-(2,4-dichlorophenyl)-4-hydroxy-2-chlorotetracycline. This product is oxidized directly with chromic anhydride in acetic acid, getting after purification by chromatography on silica furanone in the form of white crystals with a melting point 99oC.

Stage c). Getting 7-chloromethyl-7-(2,4-dichlorophenyl)-1,4,6-dioxaspiro[4,4]nonane.

Obtained in step b) furanone (4,2 g) in toluene (50 ml) is heated under reflux in the presence of ethylene glycol (6.5 ml) and toluensulfonyl what they hydroxide, then diluted with water, extracted with ether and concentrated. Get a solid white color with a melting point 99oC.

Step d). The connection 13.

The halide of step (C) (5 g) in dimethyl sulfoxide (20 ml) is heated at 170oC in the presence of triazolinone within 6 hours. The medium is poured into water, extracted with ethyl acetate, concentrated and purified by chromatography on silica. Emit a pale-yellow crystals (3.6 g) after recrystallization in a mixture of ethyl acetate and heptane with a melting point 123oC.

Example VI. Obtaining 1-(4-chloro-2-(2,4-dichlorophenyl)-tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. Connection N 14a and 14b.

Stage a). Getting 2-(2,4-dichlorophenyl)-1,4,5-trichloro-2-pentanol.

Obtained in stage a) of example 1 chlorhydrin in solution with dichloromethane (150 ml) is treated with chlorine gas (13,4 g) at -15oC. Then the medium is treated with a solution of sodium bisulfite 37% (15 ml), washed with water, dried and evaporated. Get the crude product as a colourless oil (49,7 g) containing about 70% of the desired product as a mixture of two diastereoisomers.

Stage b). Obtain 1-(2,4 - dichlorophenyl)-1-(2,3-dichloro-1-propanol)oxirane.

-3moles/l (12 ml) at ambient temperature. The precipitate is filtered and the methanol solution is evaporated. The residue is purified by chromatography on silica. Get colorless oil (7.4 g).

The second way is to obtain the solution obtained in stage a) of example 1 chlorhydrin (19.9 g) in methanol (75 ml) and in the processing solution of potassium hydroxide (4.9 g) in methanol (20 ml) at ambient temperature. After filtration of insoluble substances and evaporation receive epoxy resin (17.1 g) in the form of a yellow oil. Epoxy resin is treated with chlorine to obtain a stable yellow color (10,1 g) at -15oC. Then the medium is washed with a solution of sodium bisulfite, water, and then evaporated in vacuum. Receive a yellow oil (20,8 g) consisting of a mixture of two diastereoisomers in the ratio of 45/55.

Stage C). Obtaining 1-[4-chloro-2-(2,4-dichlorophenyl)-tetrahydro-2-furylmethyl]-1H-1,2,4-triazole.

Obtained in step b) epoxide (61,7 g) in butanol-1 (0.5 l) were heated at 90oC for 6 hours in the presence of triazolinone (18.6 g). Mineral precipitate is filtered and the butanol is evaporated. The residue is purified by chromatography on silica (eluent 48% ethyl acetate /SUP>C, then the second diastereoisomer 14b with a melting point 97oC. the Mixture is 50/50 14a and 14b has a melting point 90oC.

Example VII. Obtaining 1-[4-oxo-2(2,4-dichlorophenyl)-tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. The connection 15.

Alcohol 2a (37,7 g) is added at -60oC in a solution of DMSO (17 ml) in dichloromethane (120 ml), treated at -60oC solution triperoxonane anhydride (25,4 ml) in dichloromethane (60 ml). After 30 minutes at -60oC bring the temperature to ambient temperature, then add triethylamine (48 ml). The medium is poured into water, extracted with dichloromethane and evaporated. Crystallization in ether to obtain white powder with a melting point 91oC.

Example VIII. Obtaining 1-[4,4 - dichloro-2-(2,4-dichlorophenyl)-tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. Connection N20.

A mixture of ketone 15 (3.1 g), pentachloride phosphorus (2.3 g), dichloromethane (30 ml) containing chloride triethylmethylammonium (0.25 g), stirred for 2 hours at ambient temperature until the disappearance of the original product. The medium is evaporated, diluted with water (100 ml), neutralized with sodium bicarbonate and extracted with ether. After drying and evaporation of oily OST the melting point 138oC.

Example IX. Obtaining 1-[4-dimethylamino-2-(2,4-dichlorophenyl)tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. The Compound N 16.

In a solution of potassium hydroxide (0.24 g) and dimethylamine hydrochloride (1,05 g) in methanol successively added the ketone from example III, then cyanoborohydride sodium (0.24 g). After 15 hours, the medium is diluted with water, extracted with ether. The target product is extracted from the organic phase hydrochloric acid 6 N (3 x 20 ml). After neutralization, extraction and chromatography on silica produce the target product (1.6 g) in the form of oil, pale yellow (50/50 mixture of the two isomers).

Example X. Obtaining 1-[4-methoxyimino-2-(2,4-dichlorophenyl)tetrahydro-2-furylmethyl]-1H-1,2,4-triazole. Connection 17.

The ketone from example III (2 g) in ethanol (30 ml) is heated under reflux in the presence of hydrochloride of methoxylamine (5.8 ml of a 25% aqueous solution) for 2 hours. Wednesday diluted with water, extracted with dichloromethane and evaporated. The product distinguish crystallization from a mixture of simple diisopropyl ether and heptane in the form of a white powder with a melting point 108oC (mixture of two geometric isomers).

Similarly prepare of the is and the following illustrate the use of compounds according to the invention as fungicides.

In these examples, the spraying of solutions or suspensions of active substances is carried out under such conditions that the spray solution or suspension at a concentration of 1 g/l, on average, corresponded to the application of approximately 2 micrograms of active ingredient per cm2the leaves of a plant.

In the conditions of example XI and the following compounds did not show phytotoxicity.

In these examples, it is believed that the product provides complete protection from fungal diseases, when the protection is at least 95% protection is good when it is at least 80% (but less than 95%), as a pretty good, when she is at least 70% (but less than 80%), medium when it is at least 50% (but less than 70%).

In the present description, excepting the opposite indications and indications regarding the effectiveness, the percentages are weight percentages. When interest is expressed relative to stoichiometry, we are talking about molar percent. With regard to concentrations, some of which are expressed in ppm (part per million), which corresponds mg/l

Example XI. Test in vivo on Botrytis cinerea on tomato.

E is/BR> the investigated active substance 60g

-Tween 80 (surfactant), consisting of oleate polyoxyethyleneglycol derived sorbitan, diluted to 10% concentration with water 0.3 ml

add 60 ml of water

Then, this aqueous emulsion is diluted with water to obtain the required concentration.

Planted in the greenhouse tomato varieties Marmande at the age of 30 to 40 days is treated by spraying water emulsions (called pulp) described above and having different concentrations of the test compounds. The test is carried out twice for each concentration.

After 24 and 48 hours, the leaves are cut and placed in two Petri dishes (diameter 14 cm) at the bottom of which the pre-wet laid filter paper discs (5 pieces in each Cup).

Then the inoculum is injected with a syringe and put three drops on a leaf of the spore suspension. Spore suspension of Botrytis cinerea from a culture in the age of 15 days, which is suspended in the nutrient solution (100000 units/cm3).

Control is carried out through 3 to 6 days after infection by comparing with the untreated control sample.

In these conditions observed at the dose of 1 g/l good is the natural enemy conditions on Erysiphe graminis on barley (powdery mildew of barley).

Barley in cups, sown in fertile soil, treated at the stage of 10 cm height by spraying water emulsion (called pulp) with the following concentrations. The test is repeated twice. After 24 hours optivault barley plants with spores Erysiphe graminis, and the dusting is performed with the use of diseased plants.

The test carried out in 8 to 14 days after infection. Under these conditions, observe the following results: at a dose of 1 g/l good or complete protection with compounds 1a, 1b, 1a + 1b, 2a, 2b, 3a, 3b, 3a + 3b, 4a, 4b, 5a, 5b, 6a, 6b, 7a + 7b, 8a, 8b, 13, 14a, 14b, 14a + 14b, 15, 17, 19, 20.

Example XIII. Test in vivo on Puccina recondita causing rust of wheat.

Wheat in cups, sown in fertile soil, treated at the stage of 10 cm height by spraying water emulsion (called the pulp) of the same connection, as described in example XI, and with different concentrations of the test compounds. The test is carried out twice for each concentration.

After 24 hours water spore suspension (50000 CPS/cm3) sprinkle of wheat; the suspension obtained from infected plants. Then the wheat was incubated for 48 hours in an incubation chamber p is sustained fashion humidity is reduced to 60% of Checking the condition of the plants is carried out in the period from the 11th to the 15th day after infection by comparing with the untreated control sample.

At the dose of 1 g/l protection a good or complete with compounds 1a, 1b, 1a + 1b, 3a, 3b, 3a + 3b, 5b, 6b, 7a, 7a + 7b, 8b, 12b, 13, 14a, 14b, 14a + 14b, 17, 19, 20.

Example XIV. Test in vivo on Piricularia oryzae, which causes piricularia rice (Rice Blast).

Rice in cups, sown in a mixture of 50/50 peat enriched with pozzolan process at the stage of 10 cm height by spraying the above-mentioned aqueous emulsion (called pulp) with a concentration specified below. The test is carried out twice. After 48 hours they process by applying to the leaves of a suspension of spores obtained in pure culture.

Checks carried out 8 days after infection. Under these conditions, observe the following results: at a dose of 1 g/l are good or complete protection with compounds 1a, 1b, 1a + 1b, 3a, 3b, 6a, 6b, 8a, 8b, 9a, 9b, 10b, 11a, 11b, 12a, 12b, 14a, 14b, 14a + 14b, 15, 20.

Example XV. The laboratory testing of seed and soil fungi.

Investigate the effect of the compounds according to the invention the following fungi that cause diseases of crops and other plants:

1) Pyrenophorae avenae

2) Septoria nodorum

3) Helminthosporium teres

4) Fusarium roseum

5) Fusarium nivale

6) Fusarium culmorum

7) Rhizoctonia cerealis

8) Septoria resistance to carbonated and cyclic imides

11) Pseudocercosporella herpotrichoides

12) Fusarium oxysporum F. sp. melonis

13) Rhizoctonia solani

14) Helminthosporium gramineum

The numbers before the names will be used to denote these fungi in the table (II).

For each test perform the following operations: a nutrient medium consisting of potato, glucose and agar (PDA environment), injected into the supercooled in a series of Petri dishes (20 ml per Cup) after sterilization in an autoclave at 120oC.

When filling the cups in a supercooled environment enter the acetone solution of the active substance to obtain the required final concentration.

As control samples used similar to the previous Petri dishes, pour the same quantity of the nutrient medium, containing no active ingredient.

After 24 or 48 hours in each Cup was placed a piece of mycelium from the above culture of the same fungus.

Cups are stored for 2 to 10 days (depending on the test fungus) at a temperature of 22oC and then compare the growth of fungi in the cups containing the tested active substance, with the growth of the fungus in the sample Cup.

Thus, for each isany in the following table 3.

1. Derivatives of tetrahydrofuran of the formula I

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where X1and X2the same or different and represent hydrogen, halogen,-(C1-C4)-alkyl, hydroxy, S-(C1-C4)-alkyl, acyl, substituted with halogen, di (C1-C4-alkyl)-amino, (C1-C4)- alkoxyimino;

And phenyl, substituted 2 atoms of halogen;

R1R5hydrogen, as well as their optical isomers, racemates and diastereomers.

2. The method of obtaining the compounds of formula I, where X2corresponds to the halogen, characterized in that halogenation formula IIA

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where a phenyl, substituted 2 atoms of halogen,

R5hydrogen

Z is halogen atom,

subjected to interaction with the ORGANOMETALLIC compound of the formula IIB

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where X1, R1R4have the specified values;

M metal atom,

with the subsequent interaction of the compounds of formula IIc

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with the unsubstituted triazole in the environment of a mineral or organic base, obtained compound of formula (IId)

< / BR>
where A, R1R5X1and Tg have the specified values,

is treated with a halogen or mixed halogen in an inert solvent and obtained the x2">

3. The method of obtaining the compounds of formula I on p. 1, where X2- halogen, characterized in that the compound of formula IIC is treated with a halogen or mixed halogen in an inert solvent, and hereinafter formula p. 3, except imidazole at the stage of interaction of the compounds of formula II.

4. A method of combating fungi by treating the plants or their habitat derivative 1-[2-(2,4-dichlorophenyl)- tetrahydrofuran-2-yl-methyl] -1H,1,2,4-triazole, wherein, to increase the efficiency of the method as a function of 1-[2-(2,4 - dichlorophenyl)- tetrahydrofuran-2 - yl-methyl] -1H-1,2,4 - triazole is used as a compound of the formula I

< / BR>
in the form of an isomer with a melting point 96oWith or equimolecular mixture of isomers in the amount of 0.11 1 kg/ha

 

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< / BR>
whererepresents a single or double bond; R1represents a C1-C4alkyl; R2represents a C1-C4alkyl or C3-C6cycloalkyl; R1and R2together with the carbon atom to which they are joined, can form WITH3-C6cycloalkyl, optionally substituted stands; And represents СООR3CHO, CH2OH, COCH2HE, CONHCH2CH2OH, CONHOH or

R3hydrogen, C1-C12alkyl, which can be broken od is alkoxy, halogen, hydroxyl, C3-C6cycloalkyl, benzyloxy, fullam, phenyl, furfuryl, galopera, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, carboxyla, lower alkoxycarbonyl, cyano, C1-C4alkylthio or three (lower) alkylammonium; C3-C6alkenyl, optionally substituted by one of the following groups:1-C3alkoxy, phenyl, halogen or two WITH1-C3alkoxygroup or two halogen groups; C3-C6cyclooctyl, optionally substituted by one or two1-C3alkyl groups; C3-C10quinil, optionally substituted by phenyl, halogen or CH2IT; or the cation of an alkali metal or alkaline-earth metal (CA, BA) manganese, copper, iron, ammonium, or organic ammonium; RWITHand RDrepresent N or CH3; Represents N; COR4or SO2R5provided that when a represents a COR4or SO2R5and is a СOOR3the radical R3cannot be hydrogen or a salt-forming cation; R4represents a C1-C11alkyl, chloromethyl or phenyl, optionally substituted A5 alkyl or phenyl, optionally substituted one metalno, chloro - or nitro-group; W represents 0 or S; X represents 0, S or whenis a single bond, the group S 0; Y and Y', Z and Z' represent hydrogen, halogen, C1-C6alkyl, C1-C4hydroxy (lower) alkyl, C1-C6alkoxy, C1-C6acyloxy, benzoyloxy, optionally substituted by one or two1-C4alkyl, C1-C4alkoxygroup or halogen; C1-C4alkylthio, phenoxy,1-C4haloalkyl,1-C4haloalkoxy, nitro, cyano, C1-C4alkylamino,1-C4dialkylamino,1-C4alkylsulfonyl or phenyl, optionally substituted by one or more1-C4the alkyl, C1-C4alkoxy, halogen, or any combination of these two groups, where Y and Z are the same provided that Y and Z represent hydrogen, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and taken together, Y and Z form a ring in which YZ has the structural formula -(CH2)n- where n являе/www.fips.ru/fullimg/rupat2/19962/004.dwl/2058313-8t.gif" ALIGN="ABSMIDDLE">-=where L, M, Q, and R7each represent hydrogen, halogen, nitro, C1-C4lower alkyl, C1-C4lower alkoxy, methoxy, phenyl, phenoxy, provided that only one of the radicals L, M, Q or R7may have a value different from hydrogen, halogen, C1-C4the alkyl or C1-C4alkoxy; or a pyridine-N-oxides, when W represents oxygen or sulfur and a is COOR3; and when R1and R2not the same, the optical isomers of these compounds, except for the case when R3represents a salt-forming cation, their salts kislotoustoichivam

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CFN< / BR>
where R represents a hydrogen atom or methyl;

x represents a fluorine atom, a chlorine atom or a nitro-group;

y represents a fluorine atom or a chlorine atom;

z represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a process for the preparation of these compounds and insecticides containing as active components of these compounds

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< / BR>
The specified connection, properties, method of preparation and application are not described in literature

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