Derivatives of piperidine or an acid additive salt, fungicidal composition and method of combating fungi

 

(57) Abstract:

The essence of the invention: derivatives of piperidine derivatives of the formula

< / BR>
or their acid additive salts, where R is H, C1- C12-alkyl, C2- C6alkenyl, C2- C6-quinil, C1- C6-alkoxy, C3- C8-cycloalkyl, phenyl, naphthyl, phenylcarbinol, heterocyclyl or heterotardigrada, in which the heterocycle is a five - or six-membered ring with one or two heteroatoms selected from N, S, and R may have substituents: halogen, nitro, cyano, HE, C1- C4-alkyl, C1- C4-alkoxy, amino, C1- C4-alkoxycarbonyl, phenyl or galogenangidridy; R1is phenyl, benzyl, C3- C8-cycloalkyl, and R1may have a Deputy-halogen, C1- C4-alkyl, C1-C4-alkoxy; R2-H, methyl, one of W and X represents-CH2-, -CH2- CH2- or - O-, and the other of W and X represents-CH2- or-CH2-CH2or X is a simple chemical bond, m is 0 or 1, and n is an integer from 0 to 3. The invention relates to fungicidal compositions containing the specified connection, and to a method of combating fungi with isolee relates to certain derivatives of piperidine, the way its receipt, to compositions containing these compounds and to their use as fungicides.

In the work of DE-A-3614907 (Germany) discloses compounds of General formula:

where R is a C1-20-alkyl, C2-20-alkoxyalkyl,2-20-hydroxyalkyl,3-12-cycloalkyl,4-20-alkylcyclohexanes,4-20-cycloalkylation, aryl, halogenation,7-20-aralkyl,7-20-halogenoalkanes or7-20-aryloxyalkyl; m is 1 or 2, a n is 0 or 1, and some of these compounds show higher activity against phytopathogenic fungi than Fenpropimorph. Compounds in which m is 2, i.e. the derivatives of piperidine, substituted in the 1 - and 4-positions and n 0 are particularly preferred.

However, it was discovered that certain derivatives of piperidine, substituted in the 1 - and 3-positions, have a high activity against certain phytopathogenic fungi. Accordingly the present invention relates to the compound of General formula:

R1-(I) or its acid additive salts or complex metal salt, where R represents a hydrogen atom or optionally substituted alkyl, alkylamino, alkoxy, cycloalkyl optionally substituted alkyl, phenyl, benzyl or cycloalkyl group; R2represents a hydrogen atom or optionally substituted alkyl group; one of W and X is-CH2-, CH2CH2- or-0-, and the other of W and X is-CH2- or-CH2CH2or X is a simple chemical bond; m is 0 or 1, and n is an integer from 0 to 3.

If the proposed compounds contain alkyl, alkenylphenol or alkenylphenol substituted group, they can be linear or branched and contain up to 12, preferably up to 6 carbon atoms. Cycloalkyl group may contain from 3 to 8, preferably from 3 to 6 carbon atoms. The aryl group may be any aromatic hydrocarbon group, for example phenyl or naftilos group. Heterocyclic group may be any saturated or unsaturated ring system containing at least one heteroatom, especially preferred are rings with 5 or 6 members.

If any of the above substituting groups are optionally substituted, i.e., these substituting groups are optional, one or more of them may be the standard groups, and usually is and their structure, the activity, stability, permeability, or other useful properties. Specific examples of such substituting groups are halogen atoms, nitro, cyano, hydroxyl, cycloalkyl, alkyl, halogenation, alkoxy, halogenoalkane, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alcoolica, alkylthio, alkylsulfonyl, carnemolla, alkylamino, phenyl, phenoxy, halogenfree group. If the above substituents are, or contain alkyl replacement group, they can be linear or branched and contain up to 12, preferably up to 6, and most preferably up to 4 carbon atoms.

Preferably, when R is a hydrogen or C1-12-alkyl, C2-6-alkenyl,2-6-quinil,1-6-alkoxy, C3-8-cycloalkyl, phenyl, naphthyl, phenylcarbinol, heterocyclic or heterocyclic group, and each group is optionally substituted by one or more substituents selected from halogen atoms, nitro, cyano, hydroxyl, C1-4-alkyl, C1-4-halogenoalkanes,1-4-alkoxy, C1-4-halogenoalkane, amino1-4-alkylamino, di-C1-4<

More preferably, when R represents a hydrogen atom or a C1-12-alkyl, C2-4-alkenylphenol,2-4-alkylamino,1-4-alkoxy, C3-6-cycloalkyl, phenyl, naftalina, phenylcarbonylamino, heterocyclyl or heterocyclic group; and each of these groups is optionally substituted by one or two substituents selected from halogen atoms, nitro, cyano, hydroxyl, C1-4-alkyl, C1-4-alkoxy, amino, C1-4-alkoxycarbonyl, phenyl, halogenfree groups.

Preferably, if R1represents phenyl, benzyl or3-8-cycloalkyl group, and each of these groups is optionally substituted by one or more substituents selected from halogen atoms, nitro, cyano, hydroxyl, C1-4-alkyl, C1-4-halogenoalkanes,1-4-alkoxy, C1-4-halogenoalkane, amino, C1-4-alkylamino, di-C1-4-alkylamino, formyl, C1-4-alkoxycarbonyl and carboxyl groups.

More preferably, if R1is3-6-cycloalkyl group or phenyl or benzyl group, optionally substituted atom is an atom of hydrogen or C1-6- especially WITH1-4group.

Especially preferred subgroup of compounds of formula (I) is such a subgroup, in which R represents a hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, under, dodecyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, ethoxyethyl, ethoxymethyl, diatexites, diethoxylate, ethoxycarbonylmethyl, dichlorophenoxy-hydroxypropyl, ethynyl, propenyl, ethinyl, PROPYNYL, butoxy, methoxyethoxy, cyclohexyl, phenyl, foriener, course, dichlorophenyl, bromophenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, were, butylphenyl, methoxyphenyl, AMINOPHENYL, biphenylyl, naphthyl, hydroxynaphthyl, chlorophenylsulfonyl, tsiridis, imidazolyl, morpholinyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thienyl or tetrahydropyranyloxy; R1represents phenyl, course, were, were, propylphenyl, butylphenyl, methoxyphenyl, forebesi or cyclohexyl; R2represents a hydrogen atom or methyl group.

The compounds of formula (I) can form acid additive salts or complexes of metal salts formed by different acids and metal salts. Especially predota, especially hydrochloric acid.

Thus the compounds of formula (I) may exist in the form of various geometric isomers and diastereomers.

The invention includes both the individual isomers and their mixtures.

The present invention also relates to a method for obtaining compounds of formula (I) as defined above, or its acid additive salts or complexes of the metal salt, which is that the connection formulas

P (II) or its acid additive salt is subjected to the reaction of interaction with the compound of the formula

Y Z, where (III) if R is a-CH2R1or-CH2CH2R1and Q represents a hydrogen atom, Y is -(CO)m(CH2)nR, or if R is-HE and Q represents -(CO)m(CH2)nR, then Y is R1; Z represents a halogen atom and R, R1, R2, W, m, and n are defined above in the presence of a base; and optionally, if m and n are both equal to 0, is subjected to the conversion of compound (I) in which R is nitrophenyl, in the compound of formula (I) in which R is AMINOPHENYL; and optionally subjected to the conversion of the compound of formula (I) in which R is AMINOPHENYL, Saedinenie of the above compound of formula (I) is subjected to the reaction of interaction with the corresponding acid or salt of the metal to form the acid additive salts or complex metal salt.

Typically, the compound of formula (I) in which X represents-CH2- or-CH2CH2- produced by the reaction of compounds of formula (II) in which R is-CH2R1or-CH2CH2R1and Q is a hydrogen atom, with a compound of formula (III) in which Y is -(CO)m(CH2)nR, a Z is a halogen atom, preferably fluorine atom, chlorine or bromine, in the presence of a base such as sodium carbonate, potassium carbonate or triethylamine. In addition, the compounds of formula (I) in which m is 1, can be converted into compounds of formula (I) in which m is 0 by reaction with the corresponding regenerating agent such as alumalite lithium.

The alternate connection of the formula (I) in which X represents-0-, can be obtained by reaction of compounds of formula (II) in which R is-HE and Q is -(CO)m(CH2)nR, with the compound of formula (III) in which Y is R1a Z is a halogen, preferably fluorine, in the presence of a strong base such as sodium hydride or metallic sodium.

If m and n is 0, the compound of formula (I) in which R is nitrophenyl, can be turned into connection the mayor as palladium charcoal. The compound obtained of the formula (I) in which R is AMINOPHENYL, can then be transformed into a compound of formula (I) in which R is a course, bromophenyl, idonesia or cyanoptila through reaction with sodium nitrite in the presence of acid, such as hydrochloric for the formation of a diazonium salt, followed by reaction with the chloride of copper (I) bromide copper (I) iodide copper (I) or copper cyanide (I) in the reaction of Sandmeyer.

The proposed method is carried out in the presence of a solvent. Examples of suitable solvents are ethers, in particular tetrahydrofuran, dimethylsulfoxide and dimethylformamide. The reaction is usually carried out at temperatures from -20aboutWith up to 180aboutWith, and preferably at a temperature of from -5aboutWith up to 165aboutC.

The compounds of formula (II) in which W represents-CH2- or-CH2CH2-, R represents-CH2R1or-CH2CH2R1, Q represents a hydrogen atom, can be obtained by reaction of compounds of General formula:

(IV) where R is-CH2R1or-CH2CH2R1, a R2defined above, with a corresponding regenerating agent such as lumpy:

R (V) where R2defined above, and W represents-CH2- or-CH2CH2-; with a compound of General formula:

P L (VI), where R is a-CH2R1or-CH2CH2R1and L is a leaving group, preferably halogen, and more preferably a bromine atom, in the presence of a base, for example butylnitrite.

The compounds of formula (II) in which R represents-HE, and Q represents -(CO)m(CH2)nR1can be obtained by reaction of compounds of General formula:

(VII) where R2and W are defined above, with a compound of General formula

R(CH2)n(CO)mL' (VIII) where R is defined above and L' is a leaving group, preferably halogen, such as chlorine atom or bromine; in the presence of an appropriate base, such as sodium carbonate, potassium carbonate or triethylamine.

The compounds of formula (VII) can be obtained by the method described in: J. H. Biel, H. Z. Friedman, H. A. Leiser, and E. P. Sprengler, J. Am. Chem. Soc. 1952, 74, 1485.

The compounds of formula (II), where W represents-0-; R represents a-CH2R1or-CH2CH2R1a Q represents a hydrogen atom or sour hell
R1or-CH2CH2R1D is a protecting group such as benzyl group; and R1defined above; with a reagent that promotes the removal of the protective group D, for example by etelcharge.com or chloroethylamino.

The compounds of formula (IX) can be obtained by reaction of compounds of General formula:

(X) where D is defined above, with a compound of formula (VI) defined above, in the presence of an appropriate base such as diisopropylamide lithium.

The compound of formula (X) can be obtained by reaction of compounds of General formula:

D-NH-CH2CH2OH (XI) where D is defined above; with a compound of General formula:

Hal CH2COOCH2CH3(XII) where Hal is a chlorine atom or bromine, in the presence of an appropriate base such as sodium hydride.

Compounds of formulas III, V, VI, VIII, XI and XII are known and can be obtained by standard methods.

The compounds of formula (I) possesses fungicidal activity. In accordance with this present invention relates to a fungicidal composition comprising a carrier and as active ingredient a compound of the formula (I) or its acid additive salt or metally is in the above composition is administered a compound of the formula (I) or its acid additive salt or complex in combination with at least one carrier. This composition may contain a single compound or a mixture of several compounds. However, the different isomers or their mixtures may have different levels or spectra of activity, therefore, the composition can contain individual isomers or mixture of isomers.

The proposed composition contains from 0.5 to 95 wt. the active ingredient.

The carrier composition may be any material which is introduced together with the active ingredient in order to facilitate its application on the treated, such as plants, seeds or soil, or to facilitate its storage, transport or packaging. The specified media may be solid or liquid material, and material which in the normal state is gaseous, but may be subjected to compression to a liquid state, in addition, this carrier can be any of the standard media used for the preparation of fungicidal compositions.

Suitable solid carriers can be synthetic clays and silicates, for example naturallyi and vermiculite; aluminum silicates, for example kaolinites, montmorillonite and slyly; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydroxide of silicon and synthetic silicates of calcium or ammonium; elements, for example carbon and sulphur; natural and synthetic resins, such as coumarone resin, polyvinyl chloride, and styrene polymers and copolymers; solid polihlorvinila; bitumen; waxes, such as beeswax, paraffin wax, and chlorinated mineral; and solid fertilizers, for example superphosphates.

Suitable liquid carriers are 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 distillates, such as kerosene and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene, trichloroethane. Can also be used mixtures of different liquids.

Fungicidal compositions often are produced and transported in the form of concentrates, which are then before use dilute. To facilitate dilution is usually injected a small amount of surface-activclient composition, is a surfactant. For example, the composition may contain at least two media, one of which is a surfactant.

Surface-active agent may be an emulsifying agent, dispersing agent or wetting agent; in addition, surfactants may be ionic or nonionic. Examples of suitable surfactants are the sodium and potassium salts of polyacrylic acids and ligninsulfonate acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; esters of fatty acids of glycerol, sorbitan, sucrose or pentaerythritol; condensation products of fatty alcohols or alkyl phenols, for example p-op or p-octelnet, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, salts of alkaline or alkaline-earth metals, preferably the sodium salts of esters of sulfuric or sulfonic acids containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulfate, secondary alkyl sulphates of sodium, sodium salt from sulphonated castor oil, and arylalkylamines, sodium, such as dodecylbenzyl can be made in the form of wettable powders, Farrukh Dustov, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75 wt. the active ingredient, in addition in addition to an inert solid carrier, they contain 3-10 wt. dispersing agent and, if necessary, 0-10 wt. stabilizer or stabilizers and/or other additives, such as a sealing agent or binding agent. Dusty usually made in the form of concentrates, with a composition similar to the composition described above wettable powder but without a dispersant agent, they may be diluted by additional solid carrier comprising 10 1/2 wt. the active ingredient. Pellets are usually made with particle sizes between 10 and 100 BS mesh (1,676-0,152 mm) and using the technique of sintering and impregnation. Granules contain 75 1/2 wt. the active ingredient and 0-10 wt. additives such as stabilizers, surfactants, regulator prolonged action and binding agents. The so-called dry free flowing powders consist of relatively small granules containing a relatively high concentration of the active ingredient. Emulsifying concentrates in addition to the solvent and, if necessary, and to Sarai as stabilizers, impregnating agents and corrosion inhibitors. Suspension concentrates are usually stable, nosedusas fluid foods that contain 10-75 wt. the active ingredient, 0.5 to 15 wt. dispersing agents, 0.1 to 10 wt. suspendida agents such as protective colloid and thixotropic agents, and other additives, such as antifoams, corrosion inhibitors, stabilizers, impregnating agents and binding agents; and water or an organic liquid in which the active ingredient, generally, is not soluble in the composition may be some organic or inorganic solid salt to prevent deposition or as additives for lowering the freezing temperature of water.

In the scope of the invention also includes aqueous dispersions and emulsions, for example compositions obtained by diluting the wettable powder or concentrate water. These emulsions can be emulsions of water in oil or oil in water or viscous emulsions with a consistency similar to mayonnaise.

The proposed composition may also contain other ingredients, for example other compounds with herbicide, insect which may be used by the media, reporting fungicidal compounds slow release into the environment of the protected plants. Such compositions prolonged action, for example, can be introduced into the soil surrounding the roots of climbing plants, or they may include an adhesive component, contributing to the delivery of these compositions directly to the winding stem of a plant.

The present invention also relates to the use as a fungicide compounds of General formula (I), as defined above, or its acid additive salt or metal salt complex, or composition, as defined above, and to a method of combating harmful fungi, which consists in the processing of these compounds or compositions of lesions of these fungi, such as plants, seeds of these plants or the environment of growing these plants.

The present invention has a wide range of applications in order to protect cultivated plants from fungi. Typical cultivated plants that can be protected from fungi are Loozen culture, cereals, such as wheat and barley, rice and tomatoes. The duration of action of the fungicide of the present invention depends on the specific Gutsy appropriate compositions.

P R I m e R 1. Obtaining N-2'-(3-thienyl)ethyl-3-phenylethylhpiperidinyl (R Tien-3-yl; R1phenyl; R2hydrogen; W is CH2- X-CH2-; m is 0; n is 2).

(i) Obtaining 3-phenylmethylene-2-it.

To a stirred solution of 2-piperidone (40 g, 0,404 M) in tetrahydrofuran (800 ml) for 2 h at 0aboutWith added n-utility (2.5 M in hexane, 356 ml, 0,889 M). The reaction mixture was cooled to -40aboutC and for 2 h at the drop of solution was added benzylbromide (48 ml, 0,404 M) in tetrahydrofuran. Then the reaction was slowly brought to room temperature and stirred for 12 h and then was added water (100 ml) and saturated aqueous solution of ammonium chloride (100 ml) and the aqueous phase was separated and was extracted with ethyl acetate (3 x 100 ml). The combined organic phases were washed with brine (200 ml), dried with sodium sulfate and evaporated in vacuum. The obtained solid was recrystallized from toluene and got the desired product as white needle crystals (41,2 g); So pl. 120-123aboutC. Niskonapieciowej mass spectrometry showed m/e (mass/charge) of the original molecular ion M+190, which corresponds to the molecular weight of the product 190. Elemental analysis:

Calculated: 76; N 8,0; N 7,4%

Found:IDA lithium (18.6 g, 0,49 M) in tetrahydrofuran (930 mm), stirring, was added in parts obtained in stage (i) 3-phenylmethylene-2-he (23.1 g, 0,122 M). Then the reaction mixture was heated under reflux for 5 h, cooled and treated with saturated aqueous sodium sulfate. Then the reaction mixture was filtered through a pad "Hyflo" (trade mark diatomite), the pad was thoroughly washed with ethyl acetate. The solvent is evaporated in vacuo, and the residue was distilled at 0.05 mm RT.article T.Kip.77-80aboutWith, resulting in a target product as a colorless transparent oily substance (16,1 g); M+found 176.

Analysis. Calculated: C AND 82.2; H 9,8; N 8,0%

Found: 81,9; N TO 9.9; N, 8.3% OF

(iii) Obtaining N-2'-3-thienyl ethyl-3-phenylethylhpiperidinyl.

A mixture of 3-phenylethylhpiperidinyl (1 g, 5,71 mm) obtained in stage (ii), 2-(3'-thiophenyl)-1-bromoethane (1,09 g, 5,71 mm) and potassium carbonate (2.37 g, 17.1 mm) in tetrahydrofuran (50 ml) was heated, with stirring, in a vessel under reflux for 2 days. Then the reaction mixture was cooled and poured into water (20 ml). Then the aqueous phase was extracted with ethyl acetate (2 x 10 ml) and the combined organic phases are washed with saline (10 ml) and dried shale, elwira with a mixture of hexane, ethyl acetate and triethylamine (45:4:1), resulting in a received N-2'-(3-thiophenyl)ethyl-3-phenylmaleimide in the form of a colorless transparent oily product (1,36 g), M+286.

Analysis. Calculated: 75,7; N, 8,1; N 4,9%

Found: 75,5; N 7,9; N 5,0%

P R I m m e R 2. Obtaining 3-phenylmethyl-N-(4'-methoxyphenyl)acetylpiperidine (R 4-methoxyphenyl; R1phenyl; R2hydrogen; W is CH2- X-CH2-; m 1; n 1).

To a solution of 3-phenylethylhpiperidinyl (1.75 g, 10 mm) obtained in example 1 (ii), and triethylamine (2.1 ml, 15 mm) in tetrahydrofuran (10 ml) at 0aboutWith one drop of solution was added 4-methoxyphenylacetylene (1,21 g, 12 mm) in tetrahydrofuran (10 ml). The resulting mixture was stirred for 2 h, the precipitate was filtered. The filtrate was washed with saturated aqueous sodium bicarbonate (5 ml), dried through a column flash chromatography on silica gel, elwira a mixture of ethyl acetate and hexane, first in the ratio of 1:1 and then 2: 1, resulting in the received 3-phenylmethyl-N-(4'-methoxyphenyl)acetyl - piperidine in the form of a slightly yellow syrup (2,23 g); M+324.

Analysis. Calculated: 78,0; H 7,8; N 4,3%

Found: 76,7; H 7,5; N 4,5%

P R I m e R 3. Obtaining N-2'-(4-methoxyphenyl)ethyl-3-penile smeshnoy suspension of lithium aluminum hydride (0.35 g; 9.28 are mm) in tetrahydrofuran (10 ml) drop by drop solution was added 3-phenylmethyl-N-(4'-methoxyphenyl)acetate - peridine (1.5 g, with 4.64 mm) obtained in example 2 in tetrahydrofuran (10 ml). The reaction mixture was heated in a vessel under reflux for 20 h, cooled and treated with saturated aqueous sodium sulfate. Then the reaction mixture was filtered through a pad "Hyflo" (brand of diatomaceous earth), and the pad was thoroughly washed with ethyl acetate. The filtrate is evaporated in vacuo, and the residue was purified using flash chromatography on a column of silica gel, elwira with a mixture of hexane, ethyl acetate and triethylamine (83: 15:2, respectively), resulting in a received N-2-(4-methoxyphenyl)ethyl-3-phenylmaleimide in the form of a colorless transparent oily product (1,15 g); M+310.

Analysis. Calculated: C of 81.5; H 8,8; N, 4.5%

Found: C of 81.5; H 8,9; N 4,9%

P R I m e R 4. Obtaining 3-phenoxy-N-phenylethylhpiperidinyl. R is phenyl; R1phenyl; R2hydrogen; W is CH2-; X is-0-; m is 0; n 1.

(i) Obtaining 3-hydroxy-N-phenylethylhpiperidinyl.

A mixture of 3-hydroxypiperidine (6 g, 59,3 mm), benzylbromide (10.1 g, 59,3 mm) and potassium carbonate (25 g) in tetrahydrofurane (150 ml) was heated, with stirring, in a vessel with reflux condenser Wali with ethyl acetate (3 x 20 ml), and the combined organic phases are washed with brine (50 ml) and dried with sodium sulfate. Then the solvent is evaporated in vacuo, and the residue was purified using flash chromatography on a column of silica gel, elwira with a mixture of hexane:ethyl acetate and triethylamine 35:14:1, resulting in a received target product as a colorless oily substance (9 g), M+192.

Analysis. Calculated: C 75,3; H 8,9; N, 7.3% OF

Found: C to 75.7; H 9,6; N 7,4%

(ii) Obtaining 3-phenoxy-N-phenylethylhpiperidinyl.

The hydrate of sodium (60% dispersion in mineral oil, of 0.47 g, 11.7 mm) in dimethylformamide (20 ml) was added 3-hydroxy-N-phenylmaleimide (1.5 g, 7.8 mm) obtained in stage (i) in dimethylformamide (10 ml). The reaction mixture was heated at 50aboutWith as long as you do not stop bubbling, then added florabunda (1.1 ml, 1.1 g), the reaction mixture was heated for 2 days at 75aboutC. Then the mixture was cooled, added to water (600 ml) and was extracted with toluene (4 x 70 ml). The combined extracts were dried with sodium sulfate and evaporated in vacuo, then the residue was purified using flash chromatography on silica gel, elwira with a mixture of hexane, ethyl acetate and triethylamine (70:28:2) sootvetstvenno+268.

Analysis. Calculated: C of 80.9; H 7,9; N, 5.2%

Found: C of 80.9; H 7,8; N 5.3%

P R I m e R 5. Obtain N-benzyl-3-(2-phenyl)ethylpiperidine (R is phenyl; R1phenyl; R2hydrogen; W is CH2- X-CH2CH2-; m is 0; n 1).

(i) Obtaining 3-(2'-phenyl)ethylpiperidine-2-it.

A solution of n-utility in hexane (2.4 M, 190 ml of 0.48 ml) was added, with mechanical stirring, a drop of over 90 min to a solution of 2-piperidine (21,4 g, 0.22 M) in tetrahydrofuran (430 ml) at 0aboutC. the Mixture is stirred for 1 h, and then cooled to -40aboutC. then drop by drop in the course of 1 h was added a solution of 2'-bromoethanol (40,0 g, 0.22 M) in tetrahydrofuran (100 ml). The resulting reaction mixture was slowly heated to room temperature and stirred for 3 hours After addition of saturated aqueous ammonium chloride (200 ml) and water (200 ml) the aqueous phase was extracted with ethyl acetate (3x200 ml). The combined organic phases are washed with brine (250 ml), dried with sodium sulfate, evaporated in vacuo and obtained oily substance. This substance was purified using flash chromatography on a column of silica gel, elwira first with petroleum ether, and then with a mixture of methanol, ethyl acetate and triethylamine (49:49:2), and received CE the Analysis. Calculated: C of 76.8; H 8,4; N, 6.9% OF

Found: C 76,1; H 8,5; N 7,1%

(ii) Obtaining 3-(2'-phenyl)ethylpiperidine.

3-(2'-Phenyl)ethylpiperidine-2-he (31 g, 0.15 M) obtained in stage (i) was added in portions to a stirred suspension of lithium aluminum hydride (23.1 g, and 0.61 M) in tetrahydrofuran (1000 ml). The resulting reaction mixture was heated in a vessel under reflux for 24 h, then was cooled to 5aboutAnd was treated with saturated aqueous sodium sulfate. Obtained suspension was filtered through Hyflo (trade mark diatomaceous earth), and this Hyflo pad was thoroughly washed with ethyl acetate. After evaporation of the resulting filtrate in vacuo followed by purification by flash chromatography on a column of silica gel (eluent-ethyl acetate: methanol:triethylamine 49:49:2) was obtained target compound in the form of a colorless transparent oily product (23.7 g); M+189.

Analysis. Calculated: C 82,5; H, 10.0; N, 7.4% OF

Found: C 81,1; H 10,0; N 7,9%

(iii) Obtaining N-benzyl-3-(2'-phenyl)ethylenediimine.

A mixture of 3-(2'-phenyl)ethylpiperidine (2.0 g, 10.5 mm) obtained in stage (ii); benzylbromide (1.8 g, 10.5 mm) and potassium carbonate (4.35 g, 31,5 mm) in tetrahydrofuran (50 ml) was heated in a vessel with reflux condenser, stirring of Priya with ethyl acetate (3 x 50 ml), dried with sodium sulfate and evaporated in vacuum. The obtained oily substance was purified using flash chromatography on a column of silica gel, elwira with a mixture of hexane and triethylamine (98:2), and received the target connection in the form of a colorless transparent oily product (2.2 g); M+279.

Analysis. Calculated: C 86,0; H 9,0; N 5,0%

Found: C 86,2; H 9,2; N, 5.4% OF

P R I m e R 6. Obtaining N-(4-Chlorobenzyl)-3-phenylethylenediamine (R 4-chlorophenyl; R1phenyl; R2hydrogen; W is CH2CH2- X-CH2-; m is 0; n 1.

(i) Obtaining 3-phenylethylenediamine-2-it.

A solution of n-utility in hexane (2.5 M, 178 ml, 0,444 M) was added drop by drop to a mechanically stirred solution of hexahydroazepin-2-it (22,8 g, 0,202 ml) in tetrahydrofuran (400 ml) for 90 min at 0aboutWith, the Solution stirred for 3 h, and then cooled to -50aboutC. and then for 1 h was added drop by drop benzylbromide (24 ml, 0,202 M) in tetrahydrofuran (100 ml), the reaction mixture is slowly brought to room temperature and was stirred for 15 hours After adding water (100 ml) and saturated aqueous ammonium chloride (10 ml) the aqueous phase was extracted with ethyl acetate (3 x x100 ml). United organically on a column of silica gel (eluent-ethyl acetate:methanol 25:1) received a solid product, after recrystallization from benzene/hexane received target compound as white solid (10.3 g). So pl. 99-104aboutS; M+203.

Analysis. Calculated: C of 76.8; H 8,4; N, 6.9% OF

Found: C 76,9; H 8,4; N, 6.8% OF

(ii) Obtaining 3-phenylethylenediamine.

To a stirred suspension of lithium aluminum hydride (5,19 g, 137 mm) in tetrahydrofuran (300 ml) was added parts 3-phenylethylenediamine-2-it (a 9.25 g, 45,6 mm) obtained in stage (i). The resulting reaction mixture was heated in a vessel under reflux for 7 h, then cooled and treated with saturated aqueous sodium sulfate. The resulting suspension was filtered through a pad Hyflo (trade mark diatomaceous earth) pad was thoroughly washed with ethyl acetate. After evaporation of the filtrate followed by distillation on a Kugelrohr at 0.05 mm RT.article and the temperature of the furnace 100aboutWith the received target compound in the form of a colorless transparent oily product (6.8 g); M+189.

Analysis. Calculated: C 82,5; H 10,1; N 7,4

Found: C 81,4; H 10,4; N, 6.8% OF

(iii) Obtaining N-(4-Chlorobenzyl)-3-phenylethylenediamine.

A suspension of potassium carbonate (2.37 g, 17.1 mm) in a solution of 3-phenylethylenediamine (1.08 g, 5,71 mm), POLIKLINIKA, stirring during 1 day. Then the reaction mixture was cooled and added to water (25 ml). The aqueous phase was extracted with ethyl acetate (3 x 20 ml) and the combined organic phases are washed with saline (20 ml). After drying with sodium sulfate and evaporation in vacuum was obtained oily product, which was purified using flash chromatography on a column of silica gel, elwira with a mixture of hexane, ethyl acetate and triethylamine (70: 28: 2), was obtained target compound in the form of colorless transparent oily product (1,21 g); M+313/315.

Analysis. Calculated: C 76,5; H 7,7; N 4,5%

Found: C of 76.8; H 7,7; N 4,9%

P R I m e R 7. Obtain N-(4-bromobenzyl)-2-(4-tert-butylphenylmethyl)stock research

(R 4-bromophenyl; R14-tert-butylphenyl; R2hydrogen; W is-0-; X is-CH-; m is 0; n 1).

(i) Obtaining N-benzylmorphine-3-one.

To a mechanically stirred suspension of sodium hydride (60% dispersion in mineral oil; and 17.6 g of 0.44 M) in toluene (800 ml) for 1 h was added a solution of N-benzylethanolamine (60,4 g, 0.40 M) in toluene (400 ml). The resulting reaction mixture was heated in a vessel under reflux for 2 h, after which the mixture was cooled to room temperature and for 30 min was added to the solution this is what it was cooled to room temperature and added to water (1000 ml). The aqueous phase was extracted with ethyl acetate (3 x 200 ml) and the combined organic phases are washed with brine (500 ml), dried with sodium sulfate and evaporated in vacuum. The obtained oily substance was purified using flash chromatography on a column of silica gel, elwira a mixture of ethyl acetate, hexane and triethylamine (70:28:2), was obtained the desired product as a yellow oily substance (32 g); M+191.

Analysis. Calculated: FROM 69.1; H 6,9; N, 7.3% OF

Found: C 68,2; H 7,1; N, 6.9% OF

(ii) Obtaining N-benzyl-2-(4-tert-butylphenylmethyl)morpholine-3-one.

A solution of N-benzylmorphine-3-one (4,46 g, 23,4 mm) obtained in stage (i), in tetrahydrofuran (25 ml) for 15 min on a drop was added to a solution of Diisopropylamine lithium (28.0 mm), obtained from Diisopropylamine (3,93 ml, 28.0 mm) and n-utility (2.5 M in hexane, 11.2 ml, 28.0 mm) in tetrahydrofuran (50 ml) while stirring at -78aboutC. the resulting solution was stirred for 45 min, and then for 10 min on a drop was added 4-tert-butylbenzylamine (6,0 ml, 32,7 mm) in tetrahydrofuran (25 ml). The resulting mixture was stirred for 90 min, and then heated to room temperature. After adding water (25 ml) and saturated aqueous ammonium chloride (25 ml) water passsive sodium sulfate and evaporated in vacuum. After treatment, the flash-chromatography on a column of silica gel (eluent-hexane:ethyl acetate 1:1) was obtained target compound in the form of slightly yellowish transparent oily product (5.29 g); M+337.

Analysis. Calculated: C to 78.3; H 8,1; N 4.2%

Found: C to 76.6; H 8,0; N 4,4%

(iii) 2-(4-Tert-butylphenylmethyl)morpholine, hydrochloride.

To a stirred solution of N-benzyl-2-4-tert-butylphenylmethyl of the research (to 8.94 g, 27,7 mm) obtained in stage (ii), in 1,2-dichloroethane (100 ml) at 0aboutWith added in a steady stream 1-chloroethylphosphonic (2,98 ml, 27,7 mm). The reaction mixture is stirred for 20 min, and then heated in a vessel under reflux for 135 min, then cooled and evaporated in vacuum. Then added methanol (100 ml) and the mixture was heated in a vessel under reflux for 1 h, after which the mixture was cooled, evaporated in vacuum and dissolved in chloroform (200 ml). The resulting solution was washed with saturated aqueous sodium bicarbonate (20 ml), dried with sodium sulfate and evaporated in vacuum. The obtained solid resinous substance was recrystallized from a mixture of chloroform and diethyl ether and was obtained target compound in the form of white Tverdov is 6,2; H 8,7; N 5,0%

(iv) Obtaining N-(4-bromobenzyl)-2-(4-tert-butylphenylmethyl)of the research.

A mixture of (4-tert-2-butylphenylmethyl)morphologicaland (1 g, 3.75 mm) obtained in stage (iii), 4-bromobenzylamine (1.07 g, 4.3 mm) and potassium carbonate (1.78 g, 12.9 mm) in dimethylformamide (50 ml) was heated at 110-130aboutWith stirring during 3 days. Then the reaction mixture was cooled and added to water (50 ml). The solution was extracted with ethyl acetate (5 x 20 ml). The combined organic extracts were washed with saline (20 ml), dried with sodium sulfate and evaporated in vacuum. After flash chromatography on a column of silica gel (eluent-hexane:ethyl acetate:triethylamine 90:8:2) was obtained target compound in the form of slightly yellowish oily product (1.50 g), M+: 401/403.

Analysis. Calculated: C, and 65.7; H 7,0; N, 3.5% OF

Found: C 65,6; H 6,5; N 3,6%

P R I m e R 8. Obtaining 3-(4-tert-butylphenylmethyl)-1-(4-nitrophenyl)piperidine

(R 4-nitrophenyl; R14-tert-butylphenyl; R2hydrogen; W is CH2- X-CH2-; m0; n 0).

A solution of para-pteronotropis (18,1 g 128 mm) in dimethyl sulfoxide (150 ml) was added to a suspension of potassium carbonate (17,7 g 128 mm) in a solution of 3-(4-tert-butylphenylmethyl)piperidine (29,7 g 128 mm) obtained is stirring. The reaction mixture was heated at 100aboutC for 26 h, and then cooled. Then the reaction mixture was poured into water (1 l) and extracted with ethyl acetate (3 x 500 ml). The combined organic extracts were dried with magnesium sulfate and evaporated. The obtained solid substance was recrystallized from a mixture of ethyl acetate and petroleum ether and was obtained target compound as yellow crystals (35,0 g) (yield 78%); So pl. 92-94aboutS, M+352.

Analysis. Calculated: C of 74.9; H, 6.8; the N 9,5%

Found: C 73,2; H 7,0; N, 9.6% OF

P R I m e R 9. Obtaining 3-(4-tert-butylphenylmethyl)-1-(4-AMINOPHENYL)piperidine

(R 4-AMINOPHENYL; R14-tert-butylphenyl; R2hydrogen; W is CH2- X-CH2-; m0; n 0).

A solution of 3-(4-tert-butylphenylmethyl)-1-(4-nitrophenyl)piperidine (2.0 g, 5,7 mm obtained in example 8) in ethyl acetate (250 ml) and ethanol (250 ml) containing 5% palladium charcoal was subjected to hydrogenation until then, until he stopped saturation. Then the reaction mixture was filtered through celite (trade mark diatomite), evaporated and obtained target product as a thick oily substance (1.8 g); yield 98% M+322.

Analysis. Calculated: C 81,9; H 9,4; N 8,7%

Found: C, 80,3; H 9,6; N, 8.2% OF

P R I m e R 10. The floor is; -CH2; X is-CH-; m is 0; n0).

To a solution of 3-(4-tert-butylphenylmethyl)-1-(4-AMINOPHENYL)piperidine (5.5 g, 17.0 mm) obtained in example 9, in concentrated hydrochloric acid (10 ml) and water (10 ml) at 0aboutC was added over 15 min a solution of sodium nitrite (1.38 in) 20.0 mm) in water (10 ml). After 30 min in a solution of copper chloride 1 (2,34 g) in concentrated hydrochloric acid (20 ml) was added an aliquot of the resulting solution (18 ml), the resulting reaction mixture was heated to room temperature. After 2 h the reaction mixture was heated to 60aboutC for 10 h, and then cooled and distributed between water and chloroform. The aqueous phase was extracted with chloroform and the combined phases were dried with magnesium sulfate and evaporated. The obtained solid residue was chromatographically on silica gel, elwira chloroform, and received the target compound as a slightly orange solid product (2,71 g); yield 93% So pl. 102-104aboutC. M+341/342.

Analysis. Calculated: C 77,3; H 8,3; N 4,1%

Found: C 76,9; H 8,3; N 4,1%

P R I m e R s 11-200. By methods similar to the methods described in examples 1-10, has been proposed connection are presented in table. 1. In table. 2 presents data niskonapieciowej mass spectroscopy, C, H, N analyses were solidali using the following tests.

a) Antispammeta activity against downy mildew of grapevine (Plasmopara viticolo; Pva)

The test was conducted for testing antiparasitic properties of compounds using leaf spraying. The lower surface of leaves all Loozen plants (cv. Cabernet Sauvignon) were inoculable by spraying with an aqueous suspension containing 104300 parangi/ml, for 2 days before treatment test compounds. Inoculated plants were kept for 24 h at room humidity, and then for 24 h in a greenhouse at a temperature and humidity environment. Then the lower surface of infected leaves were sprayed with a solution of active material in a mixture of water and acetone (1: 1) containing 0.04% of "tween-20" (trademark of SAS:ester of polyoxyethylenesorbitan). Spraying was performed using the sprayer moving actuator, indicating the rate of application of the composition of 1 kg/ha After spraying, the plants were returned to normal greenhouse conditions for 96 h, and then transferred to 24 hours in a high humidity environment in order to stimulate sporoobrazovanie prior to the assessment of test results. The evaluation was conducted by comparing the percentage of the area covered disputes with the banks against powdery mildew of grapevine (Plasmopara viticola; Pvp)

The test was conducted to test the direct protection of plants using leaf spraying. The bottom surface only Loozen plants (cv. Canernet Sauvignon) were sprayed with the test compound in a concentration of 1 kg of active compound per hectare using a sprayer with a moving actuator, after which the plants are kept for 24 h in normal conditions of the greenhouse, and then the lower surface of leaves was inoculable by Kristiania aqueous solution containing 104zoosporangium inside host/ml Inoculated plants are kept for 24 h in conditions of high humidity, then 5 days in normal conditions of the greenhouse, after which the plants were returned for 24 h in conditions of high humidity. The evaluation was performed by comparing the percentage of the area covered with spores, with an adequate value obtained for the control plants.

C) Immediate protective activity against Botrytis vine (Botrytis cineria; Bcp).

The test was carried out to test the direct protection of plants by spraying the leaves. The bottom surface of detached leaves of grapevine (CV. Cabernet Sauvignon) were sprayed with the test compound at a concentration of 1 kg/ha with the drive oprys what aplikasi aqueous suspension, contains 105conidia/ml after 5 days of detention in conditions of high humidity assessed the percentage of the leaf area affected by disease.

g) Activity against leaf spot of wheat Leptosphaeria nodorum; Zn.

The test was carried out to test the immediate therapeutic effects by spraying the leaves. Leaves of wheat in the phase of the first sheet (cv. Mardler) was inoculable by spraying aqueous suspensions containing 1x106spores/ml Inoculated plants are kept for 24 h before treatment in the room with high humidity. Then the plants were sprayed with a solution of the test compound in a concentration of 1 kg/ha with aid of power sprayer described in example a). After drying, the plants were kept for 6-8 days at 20-25aboutWith moderate humidity and then evaluated the results. The evaluation was performed based on the density of the defeat leaves compared with the control plants.

d) Activity against powdery mildew of barley (Erysiphe graminis f. sp. hordei. Eg.).

The test was carried out to test the immediate therapeutic effects by spraying the leaves. Leaves of seedlings of barley (CV. Golden Promis) was inoculable by spraying the horses settled for the night in the greenhouse under normal conditions of temperature and humidity. Then the plants were sprayed with the test compound at a concentration of 1 kg/ha with aid of power sprayer. After drying, the plants were returned to the chamber at 20-25aboutC and normal humidity for 7 days, and then evaluated the results of the experiment.

The evaluation was performed by comparing the percentage of the area covered with spores, with an adequate value obtained for the control plants.

(e) Activity against brown rust of wheat (Puccinia recondita; Pr).

The test was carried out to test the direct protection of plants by spraying the leaves. Seedlings of wheat (CV. Brigand) were grown to stage 1-1,5 sheet. Then the plants were sprayed with the test compound at a concentration of 1 kg/ha with aid of power sprayer described in example a). Compound used in the form of solutions or suspensions in a mixture of acetone and water (50:50 vol/vol) containing 0.04% of a surfactant ("Ivin-20" brand).

After 18-24 h after treatment, the seedlings were inoculable by spraying the plants from all sides with an aqueous suspension containing spores in a concentration of 105spores/ml After 18 h after inoculation the plants were kept in high humidity conditions and at 20-22aboutC. Then races who you experiment was assessed 10 days after inoculation based on the comparison of the percentage of the land, covered with spores, with the results obtained for the control plants.

g) Activity against pyricularia rice (Pyricularia oryzae Po).

The test was carried out to test the immediate therapeutic effects by spraying the leaves. The leaves of rice seedlings (about 30 seedlings per pot) were sprayed with an aqueous suspension containing 105spores/ml) for 20-24 h before processing plant test connection. Inoculated plants were kept overnight in high humidity conditions, and then dried and sprayed with the test compound at a concentration of 1 kg/ha using the sprayer actuator, described in a). After processing the rice plants were placed in a high humidity conditions at 25-30aboutC., the Evaluation was performed 4-5 days after treatment on the basis of the density of necrotic lesions compared with the results obtained for control plants.

C). Activity against brown spots on tomato (Alternaria solani; As).

This test was performed to test the contact preventive activity of the tested compounds by spraying the leaves.

Seedlings of tomato (cv. Outdoor Girl) were grown to the stage of the second true leaf. P is used in the form of solutions or suspensions in a mixture of acetone and water (50:50 volume/volume), containing 0.04% of a surfactant (tween-20," brand).

After 21 days after treatment, the seedlings were inoculable by spraying the upper surface of the leaves with a suspension of A. Solani-conidia containing 104spores/ml 3 days after inoculation, the plants were placed in a moist room at 100% pH or approximately at this relative humidity and at a temperature of 21aboutC. Then the plants were kept in wet conditions, but not saturated humidity.

The results were evaluated 7 days after inoculation based on the density and prevalence of lesions.

and) Activity in vitro against leaf spot of wheat (Preudocercosporella herpotrichoides; Ph (I).

This test was carried out to test in vitr activity of compounds against fungi causing leaf spot of wheat.

The test compound was dissolved or suspended in acetone and added to polurakom the potato agar with molten agarose, resulting in the concentration of 100 ppm and 3.5% acetone. After the establishment of the agar Cup was inoculable using a tube with a diameter of 6 mm mycelium agar taken from the 14-day culture of P. herpotrichoides.

The cups were incubated at 20aboutC for 12 days, after which the Fs I).

This test was performed for testing the in vitro activity of compounds against sp. Fusarium causing rot of the roots and stems of plants.

The compound was dissolved or suspended in acetone and added to the potato agar with molten dextrose half fortress, resulting in the concentration of 100 ppm them 3.5% acetone. After the establishment of the agar Cup was inoculable mycelium agar taken from 7-day cultures of Fusarium sp (inoculation was performed using tubes with a diameter of 6 mm).

The cups were incubated for 5 days at 20aboutWith, and then measured the radial growth of inoculation tube.

The extent of injury plant disease in all tests was expressed as the ratio of the results obtained for the control samples, which were either not treated or were treated with diluent in accordance with the following criteria:

0 less than 50% cure of disease; 1 of about 50-80% cure disease; 2, more than 80% cure disease.

The results of this test are presented in table. 3.

1. Derivatives of piperidine derivatives of General formula I

< / BR>
where R is hydrogen or C1- C12-alkyl, C2- C6alkenyl,2- C61- C4-alkyl, C1- C4-alkoxy, amino, C1- C4-alkoxycarbonyl, phenyl or haloperoxidase;

R1is phenyl, benzyl or3- C3-cycloalkyl, and each of these groups may be substituted with halogen, C1- C4-alkyl or C1- C4-alkoxy;

R2is hydrogen or methyl;

one of W and X - CH2-, CH2-CH2- or-O-, and the other of W and X - CH2- or-CH2-CH2or X is a simple chemical bond;

m = 0 or 1;

n is a number from 0 to 3,

or their acid additive salt.

2. Derived under item 1, wherein R is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hydroxymethyl, hydroxybutyl, ethoxyethyl, diatexites, ethoxycarbonylmethyl, dichlorophenoxyacetate, ethynyl, propenyl, ethinyl, PROPYNYL, tert-butoxy, methoxyethoxy, cyclopentyl, cyclohexyl, phenyl, forfinal, chlorfenapyr, biphenylyl, naphthyl, hydroxynaphthyl, khlorfenilalanin, pyridyl, imidazolyl, morpholinyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thienyl or tetrahydropyranyloxy, R1- phenyl, chlorophenyl, were, isopropylphenyl, tertbutylphenyl, methoxyphenyl, tormentil, cyclohexyl, R2is hydrogen or methyl.

3. Fungicidal composition comprising an active ingredient and a carrier, wherein as the active ingredient it contains a piperidine derivative of General formula I

< / BR>
where R is hydrogen or C1- C12-alkyl, C2-C6alkenyl,2-C8-quinil,1-C6-alkoxy, C3- C8-cycloalkyl, phenyl, naphthyl, phenylcarbinol, heterocyclyl or heterocyclic group, in which the heterocycle group is five - or six-membered ring with one or two heteroatoms selected from nitrogen, oxygen and sulfur, and each of the groups R may have one or more of the following substituents: halogen, nitro, cyano, hydroxyl, C1-C4-alkyl, C1- C4-alkoxy, amino, C1-C4-alkoxycarbonyl, phenyl or haloperoxidase;

R1group: phenyl, benzyl or3- C8the cycle is4-alkoxy;

R2is hydrogen or methyl;

one of W and X - CH2, -CH2-CH2- or-O-, and the other of W and X - CH2-, CH2-CH2or X is a simple chemical bond;

m = 0 or 1;

n is an integer from 0 to 3,

or its acid additive salt, in the following ingredients, wt.%:

A derivative of piperidine derivatives of General formula I - 0.5 - 95

Media - 99,5 - 5

4. The composition according to p. 3, characterized in that it contains a derivative of piperidine derivatives of General formula I or its acid additive salt, where R is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hydroxymethyl, hydroxybutyl, ethoxyethyl, diatexites, ethoxycarbonylmethyl, dichlorophenoxyacetate, ethynyl, propenyl, ethinyl, PROPYNYL, tert-butoxy, methoxyethoxy, cyclopentyl, cyclohexyl, phenyl, forfinal, chlorophenyl, dichlorophenyl, bromophenyl, nitrophenyl, cyanophenyl, hydroxyphenyl, were, butylphenyl, methoxyphenyl, AMINOPHENYL, biphenylyl, naphthyl, hydroxynaphthyl, khlorfenilalanin, pyridyl, imidazolyl, morpholinyl, furyl, tetrahydrofuryl, tetrahydropyranyl, thienyl or tetrahydropyranyloxy, R1- phenyl, chlorophenyl, were, isopropylphenyl, tertbutylphenyl, the method is the, the media further includes a surfactant.

6. A method of combating fungi, wherein the treated lesion these fungi piperidine derivative of General formula I or its acid salt additive according to any one of paragraphs. 1 and 2 or fungicidal composition according to any one of paragraphs. 3 - 5 at a dose of 1 kg/ha per active ingredient.

7. The method according to p. 6, characterized in that the lesion are plants affected or damaged by fungi, seeds of these plants or the environment of growth of these plants.

 

Same patents:

The invention relates to organic chemistry, specifically to new chemical compounds, of General formula:

< / BR>
in particular 1,3-bis(2'-hydroxy-3'-morpholinopropan)-6-methyluracil(a); 1,3-bis(2'-hydroxy-3'-piperidinoethyl)-6-stands-rallu (b); 3-bis(2'-hydroxy-3'-morpholinopropan)-5-hydroxy-6-methyluracil (); 1,3-bis(2'-hydroxy-3'-piperidinoethyl)- 5-hydroxy-6-methyluracil (g); 1,3-bis(2'-hydroxy-3'-morpholinopropan)-5-(2'-hydro - XI-3'-morpholinoethoxy)-6 - methyluracil (d) and 1,3-bis(2'-hydroxy-3'-piperidinoethyl)-5-(2'-hydroxy-3'-piperidino - poxy)- 6-methyluracil (E), showing immunotropic and anti-inflammatory activity

Fungicidal tool // 2041627

Derivative research // 2038353
The invention relates to compounds of amines having a high fungicidal activity, method of their production and to their use in agriculture as fungicides

The invention relates to chemical means of protection of plants, particularly to fungicidal compositions based on the derived triazole

The invention relates to certain new herbicide carboxamide derivative, to receive them, herbicide compositions containing such derivatives and to their use in combating undesirable plant growth

The invention relates to herbicide compositions containing herbicide BIPYRIDILIUM dichloride salt as the active ingredient

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

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

The invention relates to herbicide carboxamide derivative, method for obtaining them, herbicide compositions comprising these derivatives and their use for controlling undesirable plants

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.

SUBSTANCE: invention provides substituted methyl-N-amidooxamoyl-N-phenyl-D,L-alaninates having general formula I:

where R1 and R2 represent C1-C4-alkyl, R3 and R4 either represent H, C1-C6-alkyl or form together group -(CH3)2-X-(CH2)2- wherein X is O or CH2. Compounds exhibit fungicide activity and can be used to prevent and treat plant diseases.

EFFECT: increased choice of fungicides.

5 cl, 1 tbl, 11 ex

FIELD: organic chemistry, chemical technology, fungicides.

SUBSTANCE: invention describes substituted 1-(pyridinyl-3)-2-phenoxyethanols-1 of the general formula (I):

wherein R1 means alkyl, cycloalkyl, substituted or unsubstituted phenyl; R2 and R3 mean hydrogen or halogen atom, These compounds are prepared by interaction of oxiranes of the formula (II) with phenols of the formula (III) in the presence of a base at 100-150oC. Also, invention describes a fungicide composition based on compounds said. Invention provides preparing compounds that are effective against harmful fungi.

EFFECT: improved preparing method, valuable properties of compounds.

4 cl, 1 tbl, 7 ex

FIELD: plant protection.

SUBSTANCE: invention provides composition comprising 24-36% 2,4-dichlorophenoxyacetic acid ethylhexyl ester, 3-6% 3,6-dichloropyridine-2-carboxylic acid dimethyl-C12-C14-alkylammonium salt, 10-15% oxyethylated alkylphenols or higher fatty acids, and aromatic hydrocarbons (to 100%) at weight ratio of the first component to the second (80-90):(10-20).

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

2 cl, 2 tbl, 9 ex

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