Derivatives of carbamate and fungicide agriculture

 

(57) Abstract:

Describes the derived carbamate of General formula [I]:

in which X is a halogen atom, a C1-C6alkyl group; n is 0 or an integer 1 or 2, R1is1-C6alkyl group; R2is a hydrogen atom, a C1-C6alkyl group or a benzyl group; R3is a hydrogen atom; G is an oxygen atom; Y is a hydrogen atom,

WITH1-C10alkyl group, a C2-C10alkenylphenol group2-C10alkenylphenol group, finalley group, phenyl, naphthyl, pyridium, pyridazinyl, pyrimidinyl, triazinyl, benzothiazolyl, phenyl-C1-C6alkyl group, naphthyl-C1-C6alkyl group, thienyl-C1-C6alkyl group, thiazolyl-C1-C6alkyl group, pyridyl-C1-C6alkyl group,

chinolin-C1-C6alkyl group, morpholino-C1-C6alkyl group, oxiranyl-C1-C6alkyl group, DIOXOLANYL-C1-C6alkyl group, tetrahydrofuranyl-C1-C6SUB> cycloalkyl group1-C4alkylsulfonyl group or phenyl group. Also described fungicide agriculture, containing the derived carbamate of the formula [I] as the active ingredient. The technical result consists in obtaining fungicide, providing a high inhibitory effect on plant diseases, particularly powdery mildew of wheat and grey rot of cucumbers, without negative effects on culture. 2 S. and 2 C.p. f-crystals, 25 PL.

The technical field

This invention relates to new derivatives of carbamate and fungicide for use in agriculture/horticulture containing these derivatives as the active ingredient.

The level of technology

Up to the present time have been reported many derivatives of carbamino acid, but it was not known that the derivative carbamino acid, having a simple oximetry group in the phenyl group, as the compounds of the present invention, have an excellent fungicidal activity.

The object of this invention is new derivatives of carbamate and fungicide agriculture/horticulture, containing specified protune have conducted extensive studies with the aim of obtaining a new fungicide for use in agriculture/horticulture, and as a result found that the carbamate derivatives of the present invention (hereinafter referred to as the compounds of this invention are novel compounds not described in any source, and exhibit outstanding activity as a fungicide agriculture/horticulture, and finally completed the present invention. Namely, this invention relates to a

(1) derived carbamate represented by the General formula [I]:

in which X is a halogen atom, a C1-C6alkyl group, a C1-C6alkoxygroup, C1-C6haloalkyl group or a C1-C6haloalkoxy, n is 0 or an integer from 1 to 4, R1is C1-C6alkyl group, R2is a hydrogen atom, a C1-C6alkyl group, a C2-C6alkenylphenol group, C2-C6alkenylphenol group, C1-C6alkoxygroup, C1-C6alkoxy, C1-C6alkyl group, a C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group, C1-C6alkylsulphonyl C1-C6alkyl group or a benzyl group which may be zames is ture or-NR4group [in which R4is a hydrogen or C1-C6alkyl group], Y is a hydrogen atom, a C1-C10alkyl group (the group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, a hydroxyl group, WITH3-C6cycloalkyl group, C1-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6alkylsulfonyl group, a carboxyl group, a C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group, C1-C6alkoxyimino or C(O)NR5R6(where each of R5and R6that are the same or different, represent a hydrogen atom or a C1-C6alkyl group)),2-C10alkenylphenol group (this group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, a hydroxyl group, a C1-C6alkoxygroup, amino, mono-C1-C6The SUB> haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different, represent a hydrogen atom or a C1-C6alkyl group)),2-C10alkenylphenol group (this group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, cycloalkyl group, a hydroxyl group, a C1-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different, represent a hydrogen atom or a C1-C6alkyl group)), C3-C6cycloalkyl group (this group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C1-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6 alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different, represent a hydrogen atom or a C1-C6alkyl group)),3-C6cycloalkenyl group (this group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C6alkyl group, a C2-C6alkenylphenol group, a hydroxyl group, a C2-C6 alkenylphenol group, amino group, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkoxygroup, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different may be substituted by identical or different substituents, at least one halogen atom, a C1-C6alkyl group, a C1-C6alkoxygroup, C1-C6haloalkyl group, C1-C6alkylcarboxylic group or a C1-C6alkoxycarbonyl group), aryl group (the group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C6alkyl group, a C2-C6alkenylphenol group, C2-C6alkenylphenol group, a hydroxyl group, a C1-C6alkoxygroup, amino, mono-C1-C6 alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different, represent a hydrogen atom or a C1-C6alkyl group), a heteroaryl group (the group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C11-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different represent a hydrogen atom or a C1-C6alkyl group), aryl-C1-C6alkyl group (the aryl in said group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C6alkyl group, a C2-C6alkenylphenol group, C2-C6alkenylphenol group, fenoxaprop, which may be substituted, a hydroxyl group, a C1-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6haloalkoxy, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group, C1-C6< , which are the same or different, represent a hydrogen atom or a C1-C6alkyl group), aryl-C2-C6alkenylphenol group (the aryl in said group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C6alkyl group, a C2-C6alkenylphenol group, C2-C6alkenylphenol group, a hydroxyl group, a C1-C6alkoxygroup, amino, mono-C1-C6alkylaminocarbonyl, di-C1-C6alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different represent a hydrogen atom or a C1-C6alkyl group)), or heterocyclic C1-C6alkyl group (the heterocycle in the specified group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C6alkyl group, a C2-C6alkenyl what monography, mono-C1-C6alkylaminocarbonyl, di-C1-C6 alkylaminocarbonyl, C1-C6alkylthiol, C1-C6haloalkyl group, C1-C6alkylcarboxylic group, C1-C6alkoxycarbonyl group or C(O)NR5R6(where each of R5and R6that are the same or different represent a hydrogen atom or a C1-C6alkyl group)), and Q is a hydrogen atom, haloalkyl group, cyano, C1-C6alkyl group, a C3-C6cycloalkyl group, C1-C4alkylthiol, C1-C4alkylsulfonyl group, C1-C4alkylsulfonyl group or a phenyl group (this group may be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, C1-C4alkyl group, a C3-C4alkenylphenol group2-C4alkenylphenol group, a hydroxyl group, a C1-C4alkoxygroup, C1-C4haloalkyl group, C1-C4haloalkoxy, C1-C4alkylcarboxylic group or a C1-C4aldoxycarb the data as the active ingredient.

Symbols and terms used in this description are explained below.

The halogen atom is fluorine atom, chlorine, bromine or iodine.

Designation, such as C1-C10indicates that the number of carbon atoms in the Deputy following this designation, is from 1 to 10 in this case.

C1-C6alkyl group represents an alkyl group with straight or branched chain and may be, for example, stands, ethyl, n-propylene, isopropyl, n-bootrom, isobutyl, second-bootrom, tert-bootrom, n-Pentium, isopentyl, neopentyl, n-hexyl, 1,1-dimethylpropyl or 1,1-dimethylbutyl.

C1-C10the alkyl group may, for example, be the above C1-C6alkyl group, or a group, such as heptyl, octyl, 1,1-diethylbutyl, nonyl or decyl.

C3-C6cycloalkyl group may be, for example, a group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

C3-C6cycloalkenyl group may be, for example, a group such as 1-cyclopenten-1-yl, 2-cyclopenten-1-yl, 1-cyclohexen-1-yl or 2-cyclohexen-1-yl.

C1-C6haloalkyl group Rymer, this group, as vermeil, chloromethyl, deformity, dichloromethyl, trifluoromethyl or pentafluoroethyl.

C2-C10Alchemilla group is alkenylphenol group with a straight or branched chain and may be, for example, vinyl, 1-propanolol, 2-propanolol, Isopropenyl, 1-butanolom, 2-butanolom, 1-hexenyl or 1-oktanolom.

C2-C10Alchemilla group is alkylamino group with a straight or branched chain and may be, for example, such a group as ethinyl, 1-PROPYNYL, 2-PROPYNYL, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentenyl or 3-methyl-1-pentenyl.

C1-C6alkoxygroup is alkyloxy, in which the alkyl part has the above meaning, and can be, for example, such groups as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentane and n-hexyloxy.

C1-C6haloalkoxy is haloalkoxy in which haloalkylthio part has the above meaning, and can be, for example, such a group as formatosi, deformedarse, triptoreline or pentaverate.

C1-C6alkoxy is set, for example, such a group as methoxyimino.

C1-C6alkoxyimino C1-C6an alkyl group is alkoxyalkyl the group in which the alkoxy part and the alkyl part have the above values, and can be, for example, such a group as 1-methoxyaminomethyl.

C1-C6acylcarnitine group is alkylcarboxylic group in which the alkyl part has the above meaning, and can be, for example, such groups as acetyl, propionyl, butyryl, isobutyryl, pivaloyl or hexanoyl.

C1-C6alkoxycarbonyl group is alkoxycarbonyl the group in which the alkoxy part has the above meaning, and can be, for example, such a group as methoxycarbonyl, etoxycarbonyl, isopropoxycarbonyl or hexyloxybenzoyl.

C1-C6alkylsulphonyl C1-C6an alkyl group is alkylcarboxylic group in which the alkyl part has the above meaning, and can be, for example, such groups as 2-oxypropylene group, 3-oxobutyl group, 3-exomethylene group or a 3,3-dimethyl-2-oxobutyl group.

Aryl group Prestel.

Heterocyclic C1-C6the alkyl group is 3 to 10-membered cycle in which the alkyl part is-CH2-, -CH2CH2-, -CH2CH2CH2-, -(CH)Me-, -C(Me)2-, -CH(Et)- or similar, and the heterocyclic part has from 2 to 9 carbon atoms, from 0 to 3 nitrogen atoms, from 0 to 3 oxygen atoms and from 0 to 3 sulfur atoms, and may be, for example, such a group as pyrrolyl, furyl, thienyl, pyrazolyl, isoxazolyl, isothiazolin, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzofuran, benzothiazyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, hinely, ethanolic, morpholino, oxiranyl or doxycyclinr.

Heteroaryl group is a 5-10 membered heterocyclic aromatic ring consisting of 2-9 carbon atoms, 0-3 nitrogen atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, and may be, for example, a heterocycle, such as pyrrolyl, furyl, thienyl, pyrazolyl, isoxazolyl, isothiazolin, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzofuran, benzothiazyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, chinolin or ethanolic.

C1

Mono-C1-C6alkylamino represents a group in which the alkyl part has the above meaning, and may be a group such as methylamino, ethylamino, isopropylamino, butylamino or tert-butylamino.

Di-C1-C6alkylamino represents a group in which each alkyl parts, which are the same or different, has the above meaning, and can be, for example, such a group as dimethylamino, diethylamino, methylethylamine, methylisobutylketone or digoxigenin.

C1-C6allylthiourea represents a group in which the alkyl part has the above meaning, and may be a group such as methylthio, ethylthio, isopropylthio, butylthio or hexylthio.

C1-C6alkylsulfonyl group represents a group in which the alkyl part has the above meaning, and may be a group such as methylsulfinyl, ethylsulfinyl, isopropylphenyl, butylsulfonyl or exisulind.

C1-C6alkylsulfonyl group is methylsulphonyl, ethylsulfonyl, isopropylphenyl, butylsulfonyl or hexylsilane.

Aryl-C1-C6the alkyl group represents a group in which the aryl part has the above meaning, and the alkyl part is-CH2-, -CH2CH2-, -CH2CH2CH2-, -(CH)Me-, -C(Me)2, -CH(Et)- or similar.

Aryl-C1-C6Alchemilla group represents a group in which the aryl part has the above meaning, and Alchemilla part is-CH=CH-, -CH=SNSN2-, -C(Me)=CH-, -CH(Et)=(CH)-, -C(IU)=SNSN2- or similar.

Heteroaryl-C1-C6the alkyl group represents a group in which the heteroaryl portion has the above value, and the alkyl part is-CH2-, -CH2CH2-, -CH2CH2CH2-, -(CH)Me-, -C(Me)2-, -CH(Et)- or similar.

The best way of carrying out the invention

In tables 1-13 described specific examples of compounds of this invention represented by the General formula [I]. However, the compounds of this invention are not limited to these compounds. The references listed here are a number of compounds will be given in the subsequent description.

Scurry group, WG denotes the n-sawn group Pr-i means ISO-propyl group, BU represents n-boutelou group, Bu-i denotes isobutylene group, Bu-s is the second-boutelou group, Bu-t denotes tert-boutelou group, Hex denotes n-hexoloy group, WG-C indicates cyclopropyl group, Rap-denotes cyclopentyloxy group, Neh-denotes tsiklogeksilnogo group, and Ph denotes a phenyl group. Further, PH(4-CL) denotes the 4-chloraniline group, for example.

Some of the compounds of this invention represented by the General formula [I] have one or 2-3 double bond related E/Z isomers of these molecules and, therefore, such compounds are mixtures of E/Z isomers. Clean separate E-form and Z-form and a mixture thereof are also encompassed by the compounds of the present invention. The following pairs of compounds are geometric isomers relative to the double bond oximes part (a-80 and a-206, A-84 and a-207, A-85 and a-208, A-86 and a-209, A-286 and a-448).

Typical methods of obtaining carbamate derivative represented by the General formula [I], such as the compounds of this invention will be described below. In this case, the new compounds represented by the General formula [I] are C=N double bond and, sledovanie components by the method of purification, such as crystallization or chromatography on a column. Individual isomers and their mixtures are included in this invention.

The method of obtaining 1

where each of G, R1, R2, R3, Q, X, Y and n have the meanings given above.

The compound [I] of this invention can be obtained by the interaction of the compounds [II] and compound [III] in an inert solvent (see, for example, Jikken depending Kouza (Experimental Chemical Lecture), fourth edition, volume 20, pages 349-355 (The Chemical Society of Japan)). The compound [III] used in this way to obtain may form a salt, for example, with hydrochloric acid or sulfuric acid. The compound [III] can be obtained according to a known method (see, for example, Jikken depending Kouza, fourth edition, volume 20, pages 342-349).

As the number of compounds used in this reaction, the compound [III], respectively, is chosen in the range from 1 to 50 equivalents based on the compound [II], preferably from 1 to 10 equivalents. The inert solvent which can be used in this way to obtain that is, for example, alcohol such as methanol, ethanol, propanol or isopropanol, a simple ether, such as diethyl ether, diisopropyl ether, the coy as benzene, chlorobenzene, nitrobenzene or toluene, or water. These inert solvents can be used alone or in a mixture.

In this way receive can coexist acid, such as hydrochloric acid or acetic acid, or base, such as sodium acetate, sodium carbonate or sodium bicarbonate, and they can be used alone or in combination. The number of the respectively chosen in the range of 0.001 to 50 equivalents based on the compound [II], preferably, from 0.01 to 10 equivalents. The reaction temperature is between-10 ° C to the boiling point of the used inert solvent, and preferably ranges from 0C to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General can be from 1 to 48 hours. After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, by chromatography on a column or recrystallization, depending on the specific case.

The method of obtaining 2

where each of G, R1, R2, R3, X and n Ilkley group.

The compound [I-a] of this invention can be obtained by the interaction of the compounds [IV] and a complex ester of nitrite [V] in the presence of a base (see, for example. Organic Syntheses, volume 6, page 199 (1988)). As the number of compounds used in this reaction, the compound [V], respectively, is chosen in the range from 1 to 50 equivalents based on the compound [IV], preferably from 1 to 10 equivalents.

The base used in this way, for example, may be an alcoholate of an alkali metal such as sodium methylate, sodium ethylate or tert-butyl potassium, or an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, and the amount of the base, respectively, is chosen in the range of 0.5 to 50 equivalents based on the compound [IV], preferably from 1 to 10 equivalents.

In this way receive can be used an inert solvent that does not inhibit the progress of this process, for example, a simple ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane or dimethyl ether of diethylene glycol, halogenated hydrocarbons such as dichloromethane, chloroform, chetyrehhloristy is, what aka as methanol, ethanol, propanol or isopropanol. Data inert solvents can be used alone or in a mixture.

The reaction temperature is the interval from-70C to the boiling point of the used inert solvent, and preferably -20 to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, in General, it can be from 1 to 100 hours, preferably from 12 to 75 hours.

After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, by chromatography on a column or recrystallization, depending on the specific case.

The method of obtaining 3

where each of G, R1, R2, R3, X, Q and n have the meanings defined above, Y’ is above the value for Y with the exception of hydrogen and L is a leaving group and represents a halogen atom or a sulfonate, such as tosyloxy or mesilate.

The compound [I] of this invention can be obtained by the interaction of the compound [I-b] and the compound [VI] in the presence of a base.

In some cases, this method of obtaining can be used an inert solvent. They may be inert solvent which does not inhibit the progress of this reaction, a ketone, such as acetone, methyl ethyl ketone or cyclohexanone, a simple ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or dimethyl ether of diethylene glycol, esters such as ethyl acetate or methyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile, such as acetonitrile, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazoline or dimethylsulfoxide. Data inert solvents can be used alone or in a mixture.

The base used in this way, for example, may be an alkali metal hydride such as sodium hydride, an alcoholate of an alkali metal, such as tert-butyl potassium, or an inorganic salt such as sodium carbonate or potassium carbonate. The amount of the base, respectively, is chosen in the range of 1 to 50 equivalents in ruschival from-70C to the boiling point of the used inert solvent, preferably from 0C to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General can be from 1 to 72 hours. After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, by chromatography on a column or recrystallization, depending on the specific case.

The method of obtaining 4

where each of G, Q, R1, R2, R3X, Y and n have the meanings given above and L’ is a halogen atom.

The compound [VIII] can be obtained by halogenoalkanes compounds [VII] a known method (see, for example, Jikken depending Kouza, fourth edition, volume 19, pages 416-482 (The Chemical Society of Japan)) (phase 4.1). The compound [I-c] of this invention can be obtained by the interaction of the compound [VIII] with the compound [IX] in the presence of a base in an inert solvent (phase 4.2). Further, the compound [I-d] of the present invention can be obtained by the interaction of the compound [VIII] with tiantai salt of an alkali metal and a compound [X] in an inert solvent (see, for example, Journal of the Chemical Society of Japan, vol 87, No. 5, page 486 (1966)) (Enia, may be, for example, N-bromosuccinimide, N-chlorosuccinimide or Trichloroisocyanuric acid. The amount of halogenation agent, respectively, is chosen in the range from 0.5 to 10 equivalents based on the compound [VII], preferably from 1 to 3 equivalents. At this stage, can be used catalyst, such as azobisisobutyronitrile or benzoyl peroxide, in amounts, respectively, in the range from 0.001 to 10 equivalents based on the compound [VII], preferably from 0.001 to 1 equivalent.

The inert solvent may be a solvent that does not inhibit progress stage 4.1, and can be used, for example, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, or an aromatic hydrocarbon such as benzene or chlorobenzene.

The reaction temperature is range from 0C to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General may range from several minutes to 48 hours. After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, chromium is the number of compounds [IX], used on stage 4.2 of this method of obtaining, it is respectively chosen in the range from 1 to 50 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents.

Used may be an inorganic salt such as sodium carbonate, potassium carbonate or sodium bicarbonate, or alkali metal hydride such as sodium hydride, and the number of, respectively, chosen in the range from 0.5 to 100 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents.

Used inert solvent may be a solvent that does not inhibit the progress of the reaction at the stage 4.2, for example, a ketone such as acetone, methyl ethyl ketone or cyclohexanone, a simple ether, such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme, ester, such as ethyl acetate or methyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile, such as acetonitrile, an alcohol, such as methanol, ethanol or butanol, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazoline or dimethyl reaction is the interval from-70C to the boiling point of the used inert solvent, preferably from-10C to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General may range from several minutes to 48 hours. After completion of the reaction the desired product is recovered from the reaction system by conventional methods, and it can be cleaned, for example, by chromatography on a column or recrystallization, depending on the specific case.

Tiantai salt of an alkali metal, which can be used at the stage 4.3 of this method of receipt may be, for example, potassium cyanate or sodium cyanate. The number of used metal cyanate, respectively, is chosen in the range from 1 to 50 equivalents based on the compound [VIII], preferably from 1 to 10 equivalents, and the amount of compound [X], respectively, is chosen in the range of 1 to 100 equivalents based on the compound [VIII], preferably from 1 to 20 equivalents. The inert solvent which can be used may be a solvent that does not inhibit the progress of the reaction stage 4.3, for example, a ketone such as acetone, methyl ethyl ketone or cyclohexanone, a simple ether, such as diethyl ether, diisopropyl, halogenated hydrocarbon such as dichloromethane, chloroform or carbon tetrachloride, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile, such as acetonitrile, an alcohol, such as methanol, ethanol or butanol, or N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazoline or dimethylsulfoxide, these inert solvents can be used alone or in a mixture.

The reaction temperature is range from 0C to the boiling point of the used inert solvent. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General can be from 1 hour to 48 hours. After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, by chromatography on a column or recrystallization, depending on the specific case.

The method of obtaining 5

where each of G, R1and R3such as defined above, each of X1X2X3and X4is a hydrogen atom, a halogen atom, a C1-C6alkyl group, a C1-C6alkoxygroup, C1-C6the ilen group, C1-C6alkyl group, a C3-C6cycloalkyl group or a phenyl group (this group may be substituted by at least one halogen atom, a cyano, a nitro-group, C1-C4alkyl group, a C2-C4alkenylphenol group2-C4alkenylphenol group, a hydroxyl group, a C1-C4alkoxygroup, C1-C4haloalkyl group, C1-C4haloalkoxy, C1-C4alkylcarboxylic group or a C1-C4alkoxycarbonyl group).

The compound [I-f] the present invention can be obtained by diazotization of the compound [XVIII] the sodium nitrite in the presence of, for example, hydrochloric acid according to a known method, and the interaction of the compound [XIX] with him in the presence of, for example, sodium acetate and copper sulfate (see, for example, Organic Synthesis, volume 5, page 139 (1973)).

As the number of compounds used in this reaction, the compound [XIX] accordingly chosen in the range from 1 to 50 equivalents based on the compound [XVIII], preferably from 1 to 5 equivalents.

The solvent that can be used in this way to obtain, mo, what aka as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or dimethyl ether of diethylene glycol, esters such as ethyl acetate or methyl acetate, halogenated hydrocarbons such as dichloromethane, chloroform or carbon tetrachloride, aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene or toluene, an organic acid such as acetic acid or triperoxonane acid, or water, and these inert solvents can be used alone or in a mixture.

The acid in stage 1) diazotization, this method of receiving, instead of the above hydrochloric acid can be used in a strong acid, such as sulfuric acid, tetraberlinia acid, Hydrobromic acid or triperoxonane acid. Its amount is respectively chosen in the range of 1 to 50 equivalents based on the compound [XVIII], preferably, from 2 to 4 equivalents. Further, instead of the above sodium nitrite can be used nitrite ester such as isoamylase or methylnitrite. His number, respectively, is chosen in the range of 1 to 50 equivalents based on the compound [XVIII], preferably from 1 to 2 equival the em based, for example, the reaction temperature and amounts of reactants, and in General can range from 30 minutes to 2 hours. As compounds of copper in stage 2) the combination, in this reaction, instead of the above copper sulfate can be used salt of copper, such as copper chloride (I) or copper acetate (II). Its amount is respectively chosen in the range of 0.02 to 2 equivalents based on the compound [XVIII], preferably from 0.02 to 0.5 equivalents. The amount of sodium acetate, respectively, is chosen in the range of 1 to 50 equivalents based on the compound [XVIII], preferably from 4 to 10 equivalents. The reaction temperature is between-20C to 30C, preferably from-5C to 25C. The reaction time varies depending on, for example, from the reaction temperature and amounts of reactants, and in General can range from 30 minutes to 2 hours. After completion of the reaction the desired product isolated from the reaction medium by conventional methods, and it can be subjected to cleaning, for example, by chromatography on a column or recrystallization, depending on the specific case.

The compound [II], which is an intermediate compound for the compound [I] of this invention may be obtained, for example, according to the following known spot values, defined above.

The compound [XII] can be obtained by halogenoalkanes compounds [XI] (see, for example, Jikken depending Kouza, fourth edition, volume 19, pages 416-482 (The Chemical Society of Japan)) (stage-1). Next, the intermediate compound [II] can be obtained by the interaction of the compound [XII] with the compound [IX] in the presence of a base (for example, inorganic salts such as sodium carbonate, potassium carbonate or sodium bicarbonate, or alkali metal hydride such as sodium hydride) (stage-2). Next, the intermediate compound [II-a] can be obtained by the interaction of the compound [XII] with tiantai salt of an alkali metal and a compound [X] in the presence of an inert solvent (see, for example. Journal of the Chemical Society of Japan, vol 87, No. 5, page 486 (1966)) (stage-3).

The compounds [II] and [IV-a], which are intermediate compounds for the compounds [I] of this invention can be obtained, for example, the following known method, but is not limited to them.

where each of G, Q, R1, R2, R3, X, L’ and n have the meanings defined above, and T is1-C6alkyl group.

The compound [XVI] can be obtained by halogenoalkanes compound [XIII] (see, for example, Jikken depending Kouza is the journey of the compound [XIV] with the compound [X] and tiantai salt of an alkali metal (see, for example. Journal of the Chemical Society of Japan, vol 87, No. 5 , page 486 (1966)) (stage-2). Alternatively, the compound [XV] can be obtained by the interaction of the compound [XIV] with the compound [IX] in the presence of inorganic salts, such as sodium carbonate, potassium carbonate or sodium bicarbonate, or bases, such as alkali metal hydride such as sodium hydride (stage-3). The compound [XVI] can be obtained by reduction of compound [XV] according to a known method (see, for example, Jikken depending Kouza, fourth edition, volume 26, pages 159-266 (The Chemical Society of Japan)) (B-4). Compound [II-b] can be obtained by oxidation of compound [XVI] according to a known method (see, for example, Jikken depending Kouza, fourth edition, volume 21, page 2-23 (The Chemical Society of Japan)) (stage B-5). The compound [XVII] can be obtained by halogenoalkanes compound [XVI] according to a known method (see, for example, Jikken depending Kouza, fourth edition, volume 19, pages 416-482 (The Chemical Society of Japan)) (stage B-6).

The compound [IV-a] can be obtained by cyanidation of the compound [XVII] according to a known method (see, for example, Jikken depending Kouza, fourth edition, volume 20, pages 437-462 (The Chemical Society of Japan)) (stage B-7).

The compound [VII], an intermediate compound for the compound [I] of this invention may be obtained from R3, Q, X, Y and n have the meanings given above.

The compound [VII] the present invention can be obtained by the interaction of the compound [XI] and the compound [III] (see, for example, Jikken depending Kouza, fourth edition, volume 20, pages 349-355 (The Chemical Society of Japan)). In this case, the compound [III] used in this way to obtain may form a salt, for example, with hydrochloric acid or sulfuric acid.

The compound [XVIII], an intermediate compound for the compound [I] of this invention may be obtained, for example, the following known method, but is not limited to them.

where each of G, R1, R2, R3, L’, X1X2X3and X4have the meanings given above.

The intermediate compound [XXI] can be obtained by the interaction of the compound [XX] tiantai salt of an alkali metal and a compound [X] in an inert solvent (see, for example, Journal of the Chemical Society of Japan, vol 87, No. 5, page 486 (1966)) (stage-1). The intermediate compound [XXIII] can be obtained by nitration of the compound [XXII], for example, nitric acid, acetonitrile or sodium nitrate (see, for example, Jikken depending Kouza, fourth edition, volume 20, pages 394-399 (The Chemical Society of Japan)) (stage C-2). P(see, for example, Jikken depending Kouza, fourth edition, volume 26, pages 159-266 (The Chemical Society of Japan)) (stage C-3).

Examples

Next, methods of producing compounds of the present invention, methods of obtaining preparative forms and application are described in the examples.

The symbols used in the examples have the following meanings:

1H NMR: proton nuclear magnetic resonance

l3: Deuterated chloroform

TMS: tetramethylsilane was

s: singlet, d: doublet, t: triplet, q: Quartet, Quint: quintet, m: multiplet, width: wide, DD: double doublet

Example obtain 1

Getting 2-[4-chloro-3-(methoxycarbonylmethyl)phenyl]-2-hydroxykynurenine (compound No. a-2)

0.15 g of sodium Hydroxide and of 0.60 g of methyl N-(2-chloro-5-cyanomethylene)carbamate is added to 5 ml of ethanol and added to the mixture of 0.40 g of tert-butylnitrite at room temperature, followed by stirring for 72 hours. After the reaction solution was poured into water, extracted with ethyl acetate followed by washing with water and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on color)phenyl]-2-hydroxykynurenine in the form of a colorless viscous liquid.

1H NMR: (CDCl3/TMS (M. D.))

and 3.72 (s, 3H); 4,48 (d, 2H); 5,43 (W, 1H); 7,43-8,21 (m, 3H); 10,51, of 11.15 (W, 1H).

Example of getting 2

Getting 2-[4-chloro-3-(methoxycarbonylmethyl)phenyl]-2-methoxyisobutylisonitrile (compound No. a-3)

0.36 g of 2-[4-chloro-3-(methoxycarbonylmethyl)phenyl]-2-hydroxykynurenine and 0.54 g of a 28% solution of sodium methylate in methanol is added to 5 ml of methanol and added to the mixture of 0.49 g of methyliodide, followed by stirring at room temperature for 24 hours. The reaction solution was concentrated in vacuo, the solvent is distilled off, to the residue water is added, extracted with ethyl acetate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate = 4/1-5/1) to obtain 0.18 g of 2-[4-chloro-3-(methoxycarbonylmethyl)phenyl]-2-methoxyaminomethyl in the form of colorless crystals (melting point 104-S).

1H NMR: (CDCl3/TMS (M. D.))

3,71 (s, 3H); 4,22 (s, 3H); 4,48 (d, 2H); 5,23 (W, 1H); 7,43-with 8.05 (m, 3H).

Example of getting 3

Obtain methyl N-[2-chloro-5-(1-hydroxyimino)benzyl]carbamate (with the given 1.5 g of hydroxylamine hydrochloride, 3.0 g of sodium acetate and 5 ml of water, followed by boiling under reflux for 4 hours. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate, the organic layer is dried over anhydrous magnesium sulfate and the solvent is distilled off under reduced pressure. The resulting crystals are washed with hexane to obtain 5.2 g of methyl N-[2-chloro-5-(1-hydroxyimino)benzyl]carbamate as colorless crystals (melting point 124-127S).

1H NMR: (CDCl3/TMS (M. D.))

of 2.25 (s, 3H); 3,70 (s, 3H); to 4.46 (d, 2H); 5,31 (W, 1H); 7,27-7,63 (m, 3H).

Example 4

Obtain methyl N-[3-(1-methoxymethyl)benzyl]carbamate (compound No. A-40)

0.40 g of Methyl N-(3-acetylphenyl)carbamate are dissolved in 10 ml ethanol and added to the mixture of 0.36 g of the hydrochloride methoxyamine and 5 ml of an aqueous solution of 0.54 g of sodium acetate, followed by boiling under reflux for 8 hours. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate, the organic layer is dried over anhydrous magnesium sulfate and the solvent is distilled off under reduced pressure. The resulting crystals are washed with hexane to obtain 0.40 g of methyl N-[3-(1-methoxyimino the

2,22 (s, 3H); of 3.69 (s, 3H); 3,99 (s, 3H); 4,37 (d, 2H); 5,12 (W, 1H); 7,27-7,56 (m, 4H).

Example of getting 5

Obtain methyl N-{2-chloro-5-[1-(4-forbindelsen)ethyl]benzyl}carbamate (compound No. A-83)

0,70 g of Methyl N-[2-chloro-5-(1-hydroxyimino)benzyl]carbamate are dissolved in 10 ml of N,N-dimethylformamide and added to the mixture of 0.13 g of 60% sodium hydride while cooling on ice, followed by stirring for 1 hour. of 0.57 g of 4-Ftorangidridy dissolved in 2 ml N,N-dimethylformamide and added dropwise to the reaction mixture while cooling on ice. After completion of adding dropwise, the mixture is stirred at room temperature for 16 hours. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate followed by washing with water and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate = 5/1) to obtain 0.75 g of methyl N-{2-chloro-5-[1-(4-forbindelsen)ethyl]benzyl}carbamate (melting point 101-S) as colorless crystals.

1H NMR: (CDCl3/TMS (M. D.))

2,22 (s, 3H); of 3.69 (s, 3H); of 4.45 (d, 2H); 5,10 (W, 1H); 5.18 yl]carbamate (compound No. A-45)

10.7 g of Methyl N-[5-amino-2-Chlorobenzyl]carbamate are dissolved in 33 g of 14% hydrochloric acid, followed by stirring at room temperature for 1 hour. To the solution are added dropwise 7 ml of an aqueous solution of 3.8 g of sodium nitrite with stirring at a temperature of from 0 to 5C. The obtained Sol, page added dropwise to a mixed solvent of water/ethyl acetate/toluene (80 ml/40 ml/40 ml) of 21.7 g of sodium acetate, 2.6 g of copper sulfate and 5.9 g acetaldoxime with vigorous stirring at a temperature of from 0 to 5 ° C for 15 minutes, followed by stirring at room temperature for another 2 hours. The reaction solution is acidified with hydrochloric acid, extracted with ethyl acetate followed by washing with water and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure, the obtained crude crystal was washed with a mixed solvent of ether/ethyl acetate to obtain 2.8 g of methyl N-[2-chloro-5-(1-hydroxyimino)benzyl]carbamate as colorless crystals (melting point 124-127S).

1H NMR: (CDCl3/TMS (M. D.))

of 2.25 (s, 3H); 3,70 (s, 3H); to 4.46 (d, 2H); 5,31 (W, 1H); 7,27-7,63 (m, 3H).

Example of getting 7

Polychemical N-[2-methyl-5-(1-hydroxyimino)benzyl]carbamate are dissolved in 15 ml of N,N-dimethylformamide and added to the mixture of 0.75 g of potassium carbonate and 0.32 g of the hydrochloride of 2-chloro-6-methylpyridine, followed by stirring under heating at a temperature of from 90 to 100C for 8 hours. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate followed by washing with water and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate = 4/1) to obtain a 0.30 g of methyl N-{2-methyl-5-[1-(6-methylpyridin-2-yl-methoxy)iminoethyl]benzyl}carbamate (melting point 72-75S) as pale yellow crystals.

1H NMR: (CDCl3/TMS (M. D.))

of 2.30 (s, 3H); 2,32 (s, 3H); of 2.56 (s, 3H); of 3.69 (s, 3H); of 4.35 (d, 2H); 4,94 (W, 1H); 5,33 (s, 2H);? 7.04 baby mortality-to 7.59 (m, 6N).

The following tables 14-20 presents data 1H NMR (CDCl3/TMC, M. D.) for some examples of compounds of this invention.

Further, as reference examples, examples of making intermediates for the synthesis of compounds of this invention.

Reference example 1

Obtain methyl 4-chloro-3-(methoxycarbonylaminophenyl) benzoate

of 40.4 g of methyl 4-chloro-3-methylbenzoate, 39 g of N-bromosuccinimide and 1 g of azobisisobutyronitrile added to 300 ml of carbon tetrachloride, followed by boiling under reflux in techestva collected by filtration and the filtrate concentrated. The obtained crude crystal was washed with hexane to obtain 34.3 g of methyl 3-methyl bromide-4-chlorobenzoate in the form of white crystals. 16.0 g of the obtained methyl 3-methyl bromide-4-chlorobenzoate, 15.0 g of potassium cyanate and 35 ml of methanol is added to 200 ml of N,N-dimethylformamide, followed by stirring at a temperature of 90 ° C for 4 hours. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the obtained crude crystals washed with isopropanol with the receipt of 25.2 g of methyl 4-chloro-3-(methoxycarbonylaminophenyl)benzoate as white crystals.

1H NMR: (CDCl3/TMS (M. D.))

3,70 (s, 3H); 3,90 (s, 3H); 4,48 (d, 2H); from 5.29 (W, 1H); the 7.43 (d, 1H); 7,89 (DD, 1H); with 8.05 (s, 1H).

Reference example 2

Obtain methyl N-(2-chloro-5-hydroxymethylbenzene)carbamate

10.3 g of Methyl 4-chloro-3-(methoxycarbonylaminophenyl)benzoate are dissolved in 80 ml of anhydrous tetrahydrofuran, the resulting solution was added dropwise 100 ml of hydride diisobutylaluminum (0,95 M solution in hexane) under nitrogen atmosphere at a temperature from-50C to 30C and after complete addition the mixture was stirred at compleanno hydrochloric acid at a temperature of 0C, to the resulting solution was added water, extracted with ethyl acetate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate = 1/1) to obtain 6.5 g of methyl N-(2-chloro-5-hydroxymethylbenzene)carbamate as white crystals.

1H NMR: (CDCl3/TMS (M. D.))

2,20 (W, 1H); to 3.67 (s, 3H); 4,43 (d, 2H); with 4.65 (s, 2H); 5,26 (W, 1H); 7,21-7,37 (m, 3H).

Reference example 3

Obtain methyl N-(5-methyl bromide-2-Chlorobenzyl)carbamate

6.2 g of Methyl N-(2-chloro-5-hydroxymethylbenzene)carbamate are dissolved in 50 ml of dimethyl ether of ethylene glycol and the resulting solution was added dropwise 2.7 g of tribromide phosphorus at a temperature of-20C, followed by stirring at room temperature for 1 hour. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate followed by washing with an aqueous solution of sodium bicarbonate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled under reduced pressure to get to 6.1 g of methyl N-(5-methyl bromide-2-Chlorobenzyl)carbamate as white crystals.

1< 4

Obtain methyl N-(2-chloro-5-cyanomethylene)carbamate

2.3 g of Methyl N-(5-methyl bromide-2-Chlorobenzyl)carbamate obtained in reference example 3 was dissolved in 20 ml of N,N-dimethylformamide and the resulting solution was added of 0.43 g of sodium cyanide at a temperature of 0C. The mixture is stirred at a temperature of 0oC for 1 hour and then at room temperature for 4 hours, then to the reaction mixture, water is added, extracted with ethyl acetate and the organic solvent is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the obtained crude crystal was washed with hexane to obtain 1.3 g of methyl N-(2-chloro-5-cyanomethylene)carbamate as white crystals.

1H NMR: (CDCl3/TMS (M. D.))

3,70 (s, 3H); to 3.73 (s, 2H); of 4.44 (d, 2H); to 5.21 (W, 1H); 7.24 to 7,40 (m, 3H).

Reference example 5

Obtain methyl N-(2-chloro-5-acetylphenyl)carbamate

to 25.0 g of 4-chloro-3-methylacetophenone, to 26.6 g of N-bromosuccinimide and a catalytic amount of azobisisobutyronitrile added to 150 ml of carbon tetrachloride, followed by boiling under reflux for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the hydrated residue, 18.0 g of potassium cyanate and 38 ml of methanol is added to 150 ml of N,N-dimethylformamide, followed by stirring at a temperature of 90 ° C for 4 hours. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate) and washed with isopropyl ether to obtain 6.8 g of methyl N-(2-chloro-5-acetylphenyl)carbamate as colorless crystals.

1H NMR: (CDCl3/TMS (M. D.))

at 2.59 (s, 3H); 3,70 (s, 3H); 4,50 (d, 2H); 5,31 (W, 1H); 7,46 (d, 1H); 7,81 (DD, 1H); of 7.97 (s, 1H).

Reference example 6

Obtain methyl N-(2-chloro-5-acetylphenyl)carbamate

to 25.0 g of 4-chloro-3-methylacetophenone and 13.9 g of trichloroisocyanurate acid are suspended in 150 ml of chlorobenzene. To the resulting suspension is added a catalytic amount of azobisisobutyronitrile, followed by stirring under heating at a temperature of from 85 to 90 ° C for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and insoluble particles are collected by filtration. The filtrate is washed with water R. the deposits. The solvent is distilled off under reduced pressure, and the obtained residue, 12.2 g of potassium cyanate and 14.4 g of methanol is added to 150 ml of N,N-dimethylformamide, followed by stirring at a temperature of 90 ° C for 4 hours. After completion of the reaction, to the reaction mixture, water is added, extracted with ethyl acetate and the organic layer is dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure and the residue purified by chromatography on a column of silica gel (Wakogel C-200, eluent: hexane/ethyl acetate = 3/1). The obtained crystal was washed with isopropyl ether to obtain 6.0 g of methyl N-(2-chloro-5-acetylphenyl)carbamate as colorless crystals.

1H NMR: (CDCl3/TMS (M. D.))

at 2.59 (s, 3H); 3,70 (s, 3H); 4,50 (d, 2H); 5,31 (W, 1H); 7,46 (d, 1H); 7,81 (DD, 1H); of 7.97 (s, 1H).

Fungicides for agriculture/horticulture of the present invention contain carbamate derivatives represented by the General formula [I] as the active ingredient. When the compounds of this invention are used as fungicides in agriculture/horticulture, the active ingredient can be used in a suitable formulation form, depending on the purpose. The active ingredient is usually diluted with an inert liquid IEC, emulsifiable concentrate or granules, mixing it with surfactants and other ingredients, depending on use. Quantity for mixing the active ingredient is usually chosen depending on the specific case. However, the preferred amount is from 0.1 to 20% (wt.) for dust or granules, and from 5 to 80% (wt.) for emulsifiable concentrates or wettable powders.

Preferred examples of the carriers include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, siliceous sand, ammonium sulfate and urea, and liquid media, such as isopropyl alcohol, xylene, cyclohexanone, and methylnaphthalene. Examples of surfactants and dispersants include dinaftiletilena, salts of esters of alcohol and sulphuric acid, alkylarylsulfonate, ligninsulfonate, polyoxyethyleneglycol esters, polyoxyethylenesorbitan esters, polyoxyethylenesorbitan. Examples of adjuvants include carboxymethyl cellulose and the like.

Fungicides agriculture/horticulture of the present invention is used after diluting the above preparative Faure is and depends on the type of connection, diseases, which are struggling, trends in the development of the disease, the extent of the damage, environmental conditions, type of formulation, and so forth. For example, for direct use in the form of dust or granules, the dose of the active ingredient is chosen in the range from 0.1 kg to 5 kg, preferably from 1 g to 1 kg, 10 ar. When used in a liquid state in the form of emulsifiable concentrates or wettable powders, the dose chosen in the range from 0.1 ppm million to 10000 ppm million, preferably from 10 to 3000 ppm million

The compound of this invention in the above formulation can suppress plant diseases caused by Oomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. Specific, but not limiting examples of microorganisms are presented below. The genus Pseudoperonospora, such as Pseudoperonospora cubensis, genus Venturia, such as Venturia inaequalis, genus Erysiphe, such as Erysiphe graminis, genus Pyricularia, such as Pyricularia oryzae, genus Botrytis, such as Botrytis cinerea, genus Rhizoctonia, such as Rhizoctonia solani, genus Puccinia, such as Puccinia recondita, genus Septoria, such as Septoria nodorum and Sclerotinia, such as Sclerotinia sclerotiorum.

The compounds of this invention can be used in combination with insecticides, other fungicides, herbicides, regulators rostnik forms will be described a typical formulations of fungicides agriculture/horticulture of the present invention. In these examples,“% ” means “wt.%”.

Example formulation 1.

Dust 2% of Compound (a-30), 5% of diatomaceous earth and 93% clay mix until smooth and sprayed with getting dust.

Example formulation 2.

Wettable powder 50% of the Compound (a-31), 45% of diatomaceous earth, 2% dinaftiletilena sodium and 3% ligninsulfonate sodium mix until smooth and sprayed to obtain wettable powder.

Example formulation 3.

Emulsifiable concentrate 30% of Compound (A-109), 20% of cyclohexanone, 11% polyoxyethyleneglycol ether, 4% of Las sodium and 35% of methylnaphthalene dissolve until smooth with obtaining emulsifiable concentrate.

The preparative example form 4.

Granules 5% of Compound (A-45), 2% sodium salt of ester of lauric alcohol and sulfuric acid, 5% ligninsulfonate sodium, 2% carboxymethylcellulose and 86% of clay mix until smooth and sprayed. The resulting mixture was stirred with 20% water, granularit to 14-32 mesh using an extrusion granulator and dried to obtain granules.

Next, with reference to specific examples, the LASS="ptx2">

The test example 1

Test on preventive effect against powdery mildew of wheat 10 seeds of wheat (variety: Norin-61-go) are sown in individual plastic pots with a diameter of 6 cm and grown in the greenhouse. Seedlings of wheat that reach the stage of the second sheet, handle, in the amount of 10 ml per pot, water concentrates, wettable powders obtained according to the method of example formulations of 2, at a concentration of 500 ppm million of active ingredient and air-dried. Then the seedlings inoculant disputes Erysiphe graminis and control their development in the greenhouse. 10 days after inoculation determine the General area of damage first leaves in each pot and evaluate the effectiveness based on the criteria shown in table 21. The results are shown in table 22.

The test example 2

Test on preventive effect against causing spot blotch of wheat caused by Septoria 10 seeds of wheat (variety: Norin-61-go) are sown in individual plastic pots with a diameter of 6 cm and grown in the greenhouse. Seedlings of wheat that reach the stage of the second sheet, is treated in an amount of 10 ml per pot of water concentrates, wettable proscnt, and air-dried. Then the seedlings inoculant pycnidia Septoria nodorum and control their development in the greenhouse. 10 days after inoculation determine the General area of damage first leaves in each pot and evaluate the effectiveness based on the criteria shown in table 21. The results are shown in table 23.

The test example 3

Test on preventive effect against gray mold of cucumber 4 seed cucumber (variety: Sagami-hanziro) are sown in individual plastic pots with a diameter of 6 cm and grown in the greenhouse. Seedlings of cucumbers on reaching the stage cotyledons treated in an amount of 10 ml per pot of water concentrates, wettable powders obtained according to the method of example formulations of 2, at a concentration of 500 ppm million of active ingredient and air-dried. Then the seedlings inoculant Botrytis cinerea spores location paper disk impregnated with a suspension of spores on the surface of the cotyledons of cucumber seedlings immediately placed in a moist chamber with a temperature of -22 DEGREES. 3 days after inoculation to determine the total area of the lesion cotyledons in each pot and evaluate the effectiveness based on the criteria shown in table 24. The results are shown in table 25.

1. Derived carbamate represented by the General formula [I]

in which X is a halogen atom, a C1-C6alkyl group;

n=0, 1, or 2;

R1is1-C6alkyl group;

R2is a hydrogen atom, a C1-C6alkyl group or a benzyl group which may be substituted by a halogen atom, a C1-C6alkoxygroup, cyano;

R3is a hydrogen atom;

G is an oxygen atom;

Q is a hydrogen atom, cyano, C1-C6alkyl group, a C3-C6cycloalkyl group1-C4alkylsulfonyl group or phenyl group (pointed to by the 1, in which Y is a hydrogen atom, substituted C1-C10alkyl group (this group substituted by identical or different substituents, at least one halogen atom, cyano, C3-C6cycloalkyl group1-C6alkoxygroup, di-C1-C6alkylaminocarbonyl,1-C6alkylcarboxylic group1-C6alkoxycarbonyl group1-C6alkoxyimino)2-C10alkenylphenol group (this group may be substituted by identical or different substituents, at least one halogen atom), WITH2-C10alkenylphenol group, unsubstituted, finalley group (this group may be substituted by identical or different substituents, at least a halogen atom, a1-C6alkyl group, a C1-C6alkoxygroup), phenyl, naphthyl, unsubstituted, pyridium, pyridazinyl, pyrimidinyl, triazinyl, benzothiazolium (these groups may be substituted by identical or different substituents, at least one halogen atom, WITH1-C6alkyl group, a C1-C6alkoxygroup,1-C6ail-C1-C6alkyl group (the phenyl and naphthyl in the specified group can be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, WITH1-C6alkyl group, a C1-C6alkoxygroup,1-C6haloalkoxy,1-C6alkylcarboxylic group1-C6alkoxycarbonyl group1-C6alkoxyimino1-C6alkyl group), thienyl-C1-C6alkyl group, thiazolyl-C1-C6alkyl group, pyridyl-C1-C6alkyl group, chinolin-C1-C6alkyl group, morpholino-C1-C6alkyl group, oxiranyl-C1-C6alkyl group, DIOXOLANYL-C1-C6alkyl group, tetrahydrofuranyl-C1-C6alkyl group (the heterocycle in the specified group may be substituted by identical or different substituents, at least one halogen atom, cyano, C1-C6alkyl group, a C1-C6alkoxygroup,1-C6haloalkyl group1-C6alkylcarboxylic group).

3. Derived Kamoze be substituted by at least one halogen atom), WITH2-C10alkenylphenol group, unsubstituted, finalley group (this group may be substituted by identical or different substituents, at least WITH1-C6alkyl group, a C1-C6alkoxygroup), phenyl, naphthyl, unsubstituted, pyridium, pyridazinyl, pyrimidinyl, triazinyl, benzothiazolium (these groups may be substituted by identical or different substituents, at least one halogen atom, WITH1-C6alkyl group, a C1-C6alkoxygroup,1-C6alkylthiol,1-C6haloalkyl group), phenyl-C1-C6alkyl group, naphthyl-C1-C6alkyl group (the phenyl and naphthyl in the specified group can be substituted by identical or different substituents, at least one halogen atom, a cyano, a nitro-group, WITH1-C6alkyl group, a C1-C6alkoxygroup,1-C6haloalkoxy,1-C6alkylcarboxylic group1-C6alkoxycarbonyl group1-C6alkoxyimino1-C6alkyl group), thienyl-C1-C6alkyl group,>WITH6alkyl group, morpholino-C1-C6alkyl group, oxiranyl-C1-C6alkyl group, doxacycline-C1-C6alkyl group (the heterocycle in the specified group may be substituted by identical or different substituents, at least one halogen atom, cyano, C1-C6alkyl group, a C1-C6haloalkyl group1-C6alkylcarboxylic group).

4. Fungicide agriculture, containing the derived carbamate according to any one of paragraphs.1-3, as the active ingredient.

 

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< / BR>
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< / BR>
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