Oxime derivatives of tool for combating plant diseases, the method of obtaining hydroxykynurenine, the method of obtaining the derived oxime, hydroxykynurenine

 

(57) Abstract:

Describes the oxime derivatives of the General formula (1), where R1- H, lower alkyl, X is halogen atom, cyano, nitro, lower alkyl (which may be substituted by halogen atoms), lower alkoxy (which may be substituted by halogen atoms), phenyl, n = 0 - 2; Het A is a pyridine ring which may be substituted by halogen atom, lower alkyl, pyrimidine, pyrazinone, quinoline or hinoksolinov ring, Het In the structure of the formula(3), (4), (5), Y Is H, halogen atom, lower alkyl, which may be substituted by a halogen atom. Describe the oxime derivatives of the formula (2), where R1Is n; X is halogen atom, cyano, nitro, lower alkyl (which may be substituted by halogen atom), n = 0-2; Het In formula(3), (4), (5); Y - lower alkyl, Het - imidazole, thiazole, pyrazole nucleus, 1,2,4-triazole, thiadiazole, benzimidazole, benzthiazole, imidazo[1,2-a]-pyridine ring which may be substituted. Describes a tool for combating plant diseases containing the derived oxime, as well as ways of getting hydroxykynurenine formula (b), derived oxime of formula (1) or (2). Describes hydroxykynurenine formula (b). The new compounds of the formulas (1) and (2) obladateya relates to novel oxime derivative and agricultural chemicals, containing oxime derivatives as active ingredients, and, in particular, relates to chemicals to combat plant diseases.

Regarding derivatives, oxime, which are useful as agricultural chemicals or pesticides, Japanese patent application, first publication Hei 7-25224 authors present invention discloses, for example, that the derivatives of 4,5-substituted-1,2,3-thiadiazole effective as chemicals to combat plant diseases.

Although these derivatives are effective as of agrochemicals, the desirable development of new agricultural chemicals, which when used in smaller quantities would surpass on the effectiveness of these derivatives of thiadiazole.

Therefore, tasks that should be solved by the present invention is to provide a new derived oxime, which is quite effective for the treatment of plant diseases in small quantities, without causing damage or phytotoxicity in plants, and agricultural chemicals or pesticides containing the above derived oxime as active ingredients, in particular as chemicals DMA and investigated the biological activity of these derivatives, to meet these objectives. After a series of research this invention was completed by the discovery that oxime derivatives represented by the General chemical formulas (1) and (2) are particularly effective, showing excellent activity against various bacteria that cause plant diseases, not detecting no phytotoxicity.

This invention relates to the following oxime derivative and agricultural chemicals containing these oxime derivatives as effective agents:

(1) derived oxime represented by the following General chemical formula (1):

< / BR>
where R1denotes a hydrogen atom or a lower alkyl group; X denotes a halogen atom, a nitro-group, hydroxyl group, cyano, carboxyl group, alkoxycarbonyl group, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms), lower allylthiourea (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atom), airgroup (which may be substituted by a halogen atom or a lower alkyl Gruppo (which may be substituted by a lower alkyl group), and n denotes an integer from 0 to 3, and

Het And denotes a 6-membered nitrogen-containing aromatic cyclic structure, which contains one or two nitrogen atom, or benzododecinium nitrogen-containing aromatic cyclic structure, which may be substituted by one or two substituting groups selected from the group consisting of halogen atom, lower alkyl group, lower allylthiourea, low alkylsulfonyl, low alkoxygroup, triptoreline and ceanography, and

Het In means oxime derivatives of each cyclic structure expressed by the following formula:

< / BR>
< / BR>
< / BR>
where Y denotes a hydrogen atom, halogen atom or lower alkyl group which may be substituted by a halogen atom;

(2) derived oxime represented by the following General chemical formula (2):

< / BR>
[where R1, X, n, Het and Y are the same as defined in chemical formula (1), and With Het denotes a 5-membered nitrogen-containing aromatic cyclic structure or benzododecinium nitrogen-containing aromatic cyclic structure, which contains more than one nitrogen atom, or which may contain a sulfur atom or an oxygen atom and which can be the th nitrogen-containing aromatic cyclic structure, are groups selected from the group consisting of lower alkyl groups, lower alkylsulfonyl, triphenylmethyl, low alkoxygroup and N,N-disubstituted of sulfamoyl, substituted lower alkyl groups, and groups capable of replacing a carbon atom of the specified 5-membered nitrogen-containing aromatic cyclic structures, are groups selected from the group consisting of a halogen atom, ceanography, C1-C6alkyl group (which may be substituted by halogen atom), and C3-C6, cycloalkyl, and

WITH2-C6altergroup,2-C6altenergy, C1-C5alkoxygroup (which may be substituted by halogen atom), lower allylthiourea (which may be substituted by halogen atom), lower alkylsulfonyl (which may be substituted by halogen atom), lower alkylsulfonyl (which may be substituted by halogen atoms), amino group (which may be substituted by a lower alkyl group or a C3-C6cycloalkenyl) or triphenylmethyl, and

low alkoxycarbonyl, carbamoyl (which may be substituted by lower alkyl groups), aminomethylpropanol gruppy, alkylthiomethyl, airgroup (which may be substituted by halogen atoms) and heteroaryl (which may be substituted by halogen atoms), and

the group represented by formula-N(R2)C(=O)R3(where R2denotes a hydrogen atom or methylgroup, R3denotes a hydrogen atom, a C1-C10alkyl group (which may be substituted by halogen atoms), C3-C8cycloalkyl,2-C6altergroup and C2-C4Altenilpe, arakalgudu, a lower alkyl group (substituted amino group), arakalgudu (substituted amino group), a lower alkyl group (substituted allmineral), arakalgudu (replaced by allmineral), a lower alkyl group (substituted alkoxycarbonylmethyl), arakalgudu (replaced by alkoxycarbonylmethyl), airgroup (which may be substituted by halogen atoms, lower alkyl groups (which may be substituted by halogen atoms, lower alkoxycarbonyl, lower alkylthiophene, amino groups, nitro groups or cyano groups), heteroaryl, lower alkoxygroup,3-C6cycloalkanes, benzyloxy and alloctype)],

(3) derived Issa alkyl group;

(4) derived oxime of the formula (2), where With Het denotes tutorgroup, which is represented by the following chemical formula:

< / BR>
[where R4denotes a hydrogen atom, an amino group, a C1-C5alkoxygroup (which may be substituted by halogen atoms), lower allylthiourea (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms), or

a group of the formula-NHC(=O)R3(where R3denotes a hydrogen atom, a C1-C10alkyl group (which may be substituted by halogen atoms), C3-C8cycloalkyl,2-C6altergroup and C2-C4Altenilpe, arakalgudu, a lower alkyl group (substituted amino group), arakalgudu (substituted amino group), a lower alkyl group (substituted allmineral), arakalgudu (replaced by allmineral),

lower alkyl group (substituted alkoxycarbonylmethyl), aracelio group (substituted alkoxycarbonylmethyl), airgroup (which may be substituted by: halogen atoms, lower alkyl groups (to what Etnography or cyano groups)), heteroaryl, lower alkoxygroup or3-C6cycloalkylation, benzyloxy or alloctype) and

R5denotes a hydrogen atom, halogen atom or lower alkyl group which may be substituted by a halogen atom];

(5) derived oxime mentioned above in (4), in which R4refers to a group represented by-NHC(= O)R3(where R3denotes a hydrogen atom, a C1-C6alkyl group (which may be substituted by halogen atoms), lower C3-C6cycloalkyl, airgroup (which may be substituted by: halogen atoms, lower alkyl groups (which may be substituted by halogen atoms), lower alkoxygroup, amino groups or cyano groups), heteroaryl or lower alkoxygroup), and R5denotes a hydrogen atom;

(6) a pesticide which contains as an active ingredient, at least one oxime derivative of the above components listed in (1)-(5);

(7) a means for combating plant diseases, which contains as active ingredient, at least one oxime derivative of the above components listed in (1)-(5);

(8) means for Brezhnevite mushrooms.

The best variant embodiment of the invention

In oxime derivative represented by the General chemical formulas (1) and (2), R1denotes a hydrogen atom or a lower alkyl group. The structure of the lower alkyl group may be linear or branched, and examples of the lower alkyl groups include, for example, methylgroup, ethylpropyl, n-profilgruppen, isopropylate, n-bodygraph, isobutylparaben, sec-bodygraph and cyclopropyl, they are all in the range of C1to C4. Particularly preferred groups are a hydrogen atom and methylgroup.

In the General formulas (1) and (2) X denotes a halogen atoms, a nitro-group, hydroxyl group, cyano, carboxyl group, alkoxycarbonyl group, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms), lower allylthiourea (which may be substituted by halogen atoms) lower alkylsulfonyl (which may be substituted by halogen atoms), airgroup (which may be substituted by halogen atoms or lower alkyl groups), alloctype (which may be substituted by halogen atoms or lower alkyl group is offering the halogen include chlorine atom, the bromine atom, iodine atom and fluorine atom; examples alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group and n-propylenecarbonate group; examples of the lower alkyl groups (which may be substituted by halogen atoms include linear or branched lower C1-C4alkyl groups, such as methylgroup, telgraph, n-profilgruppen, isopropylate, n-bodygraph, isobutylparaben, second-bodygraph, tert-bodygraph, a lower alkyl group substituted with halogen), such as chlorotalpa, dipterocarp, triptoreline, diperchlorate, pentaceratops, 3,3,3-Cryptor-n-propyl group.

Examples of the lower alkoxygroup (which may be substituted by halogen atoms include a methoxy group, ethoxypropan, n-propoxylate, isopropoxy, n-butoxypropyl, isobutoxy, sec-butoxypropyl, tert-butoxypropyl, cyclopropylamino, dipterocarp.

Examples of the lower alkylthio (which may be substituted by halogen atoms) include metalcorp, ethylthiourea, n-PropertyGroup, isopropylthio, n-butylthiourea, isobutylthiazole, sec-butylthiourea, deformationof, Thrifty substituted by halogen atoms) include methanesulfonyl, acanaloniidae, n-propanesulfonyl, isopropanolamine, n-butanesulfonyl, deformities.aromatherapy and triftormetilfullerenov.

Examples of airgroup (which may be substituted by halogen atoms or lower alkyl groups) include panelgroup, 4-chlorophenylurea, 4-tailgroup and 3-pervenire.

Examples of aryloxy (which may be substituted by halogen atoms or lower alkyl groups) include fenoxaprop and 4-perperoglou.

Examples of amino groups (which may be substituted by lower alkyl groups include amino group, methylaminopropyl, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino, dimethylaminopropyl, diethylaminopropyl, di-n-propylamino, di-n-butylamino, ethylmethylamino, methyl-n-Propylamine, ethyl-n-propylamino and cyclopropylamine.

The position of substitution of X is not limited, and n denotes an integer ranging from 0 to 3. When n is 2 or 3, X may be the same or different. Preferred examples of X include a hydrogen atom, a lower C1

Het And in the General formula (1) denotes a 6-membered nitrogen-containing aromatic cyclic structure, which contains 1 or 2 nitrogen atom, or benzododecinium nitrogen-containing cyclic structure, which may be substituted by 1 or 2 replacement groups. Examples of 6-membered nitrogen-containing aromatic cyclic structures include a cyclic structure of pyridine, cyclic structure of a pyrimidine, a cyclic structure of pyrazine and a cyclic structure of pyridazine; examples benzododecinium nitrogen-containing aromatic cyclic structures include cyclic quinoline structure, a cyclic structure of hintline and a cyclic structure of cinoxacin.

Examples of substituting groups on Het And include a halogen atom, a lower alkyl group, lower allylthiourea, lower alkylsulfonyl, lower alkoxygroup, triptoreline and cyano, and, in more detail, the halogen atoms may include a chlorine atom, a bromine atom, a fluorine atom; lower alkyl groups may include linear or branched lower alkyl groups such as methylgroup, telgraph, n-profilgruppen, isopropylate, n-bodygraph, isobutyl the dust, such as methylthiourea, ethylthiourea, n-PropertyGroup, isopropylthio, n-butylthiourea, isobutylthiazole and second-butylthiourea.

Examples of the lower alkylsulfonyl include linear or branched alkylsulfonyl, such as methanesulfonyl, acanalonia, propanesulfonyl, isopropanolamine, butanesulfonyl, isobutylphenyl and second-butanesulfonyl; and examples of the lower alkoxygroup include linear or branched lower alkoxygroup, such as methoxy group, ethoxypropan, n-butoxypropyl, isobutoxide and second-butoxypropan.

A preferred example Het is pyridine-2-idgruppo, and most preferred examples of Het And include pyridine-2-idgruppo or 5-methylpyridin-2-idgruppo.

Het In General formulas (1) and (2) represented by the following formula:

< / BR>
< / BR>
< / BR>
(where Y represents a hydrogen atom, a halogen atom and a lower alkyl group (which may be substituted by a halogen atom)), and where In Het denotes a group 1,2,3-thiadiazole-4-yl, group, 1,2,5-thiadiazole-3-yl or a group 1,2,5-oxadiazol-3-yl or their halogenated derivatives, or derivatives, substituted lower alkyl group (K Y, include fluorine atom, chlorine atom, bromine atom; and examples of the lower alkyl groups (which may be substituted by halogen atoms) include lower C1-C4alkyl groups, such as methylgroup, telgraph, n-profilgruppen, isopropylate, dipterocarp and triptoreline, and the most preferred group is methylgroup.

Het With in the General formula (2) denotes a 5-membered nitrogen-containing aromatic cyclic structure or benzododecinium nitrogen-containing aromatic cyclic structure, which contains more than one nitrogen atom, which may contain a sulfur atom or an oxygen atom and which may be substituted by more than one replacement group.

Examples of 5-membered nitrogen-containing aromatic cyclic structures include a cyclic structure of pyrrole, a cyclic structure of imidazole, a cyclic structure of oxazole, a cyclic structure of thiazole, a cyclic structure of the pyrazole, a cyclic structure isoxazol cyclic structure isothiazole, the cyclic structure of 1,2,3-triazole, a cyclic structure 1,2,4-triazole, a cyclic structure of 1,2,3-oxadiazole, a cyclic structure 1,2,4-oxadiazole, a cyclic structure 1,2,5-on the ru 1,2,4-thiadiazole, the cyclic structure of 1,3,4-thiadiazole and a cyclic structure of tetrazole; and examples of their benzododecinium nitrogen-containing aromatic cyclic structures include a cyclic structure of benzimidazole, a cyclic structure of benzoxazole, benzthiazole, imidazo[1,2-a]pyridine, cyclic structure [1,2,4]triazo[1,5-a]pyridine.

Examples of groups that can replace the nitrogen atom of the group Het, include a lower alkyl group, lower alkylsulfonyl, triphenylmethyl, lower alkoxymethyl and N,N-disubstituted sulfamoyl, substituted lower alkyl groups, where examples of the lower alkyl groups include methylgroup, ethylpropyl, n-profilgruppen, isopropylate, n-bodygraph, isobutylparaben and second-bodygraph; and examples of the lower alkylsulfonyl include methanesulfonyl, econsulting, n-propanesulfonyl, isopropanolamine, n-butanesulfonyl and isobutylphenyl; examples of the lower alkoxygroup include methoxymethyl and ethoxymethyl; examples of N, N-disubstituted of sulfamoyl, substituted lower alkyl groups include dimethylsulphamoyl and diethylaluminum.

Examples of groups colney group (which may be substituted by halogen atoms), C3-C6cycloalkyl,2-C6altergroup, C2-C6Altenilpe, C1-C5alkoxygroup (which may be substituted by halogen atoms), lower allylthiourea (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms and the amino group (which may be substituted by lower alkyl groups or C3-C6cycloalkylcarbonyl) or cryptomaterial; and

the group represented by formula

-N(R2)C(=O)R3(where R2denotes a hydrogen atom or methylgroup and R3denotes a hydrogen atom, a C1-C10alkyl group (which may be substituted by halogen atoms), preferably from C1to C8), C3-C8cycloalkyl (preferably from C3to C6)2-C6altergroup, arakalgudu, a lower alkyl group (substituted amino group), arakalgudu (substituted amino group), a lower alkyl group (substituted allmineral), arakalgudu (replaced by allmineral), a lower alkyl group (substituted alkoxide lilou group (which may be substituted by halogen atoms, lowest alkoxygroup, lower alkylthiol, amino group), airgroup (which may be substituted by a nitro-group or cyano); heteroaryl, lower alkoxygroup, cycloalkanes, benzoyloxy or alloctype); and

the lower alkoxycarbonyl, carbamoyl (which may be substituted by lower alkyl groups), aminomethylpropanol (which may be substituted by lower alkyl groups), acylaminoacyl, N-alkoxycarbonylmethyl, alkylthiomethyl and airgroup or heteroaryl (which may be substituted by halogen atoms).

In practice, examples of halogen atoms include a chlorine atom, a fluorine atom and a bromine atom; examples of alkyl groups which may be substituted by halogen atoms include methylgroup, ethylpropyl, n-profilgruppen, isopropylate, n-bodygraph, isobutylparaben, n-exirgruppen, dipterocarp and triptoreline; examples3-C6cycloalkyl include cyclopropyl, cyclopentyl and cyclohexylprop; and examples2-C6altergroup include vinylgroover, allgraph, businessgroup and extirpa.

Examples of C2-C6alcininku include e is to be replaced by halogen atoms include a methoxy group, ethoxypropan, n-propoxylate, isopropoxy, n-butoxypropyl, isobutoxy, sec-butoxypropyl, n-pentyloxy, dipterocarp and cryptometer.

Examples of the lower alkylthio (which may be substituted by halogen atoms) include metalcorp, ethylthiourea, PropertyGroup, isopropylthio, butylthiourea, isobutylthiazole, sec-butylthiourea, deformationof and triptoreline.

Examples of the lower alkylsulfonyl (which may be substituted by halogen atoms) include methanesulfonyl, econsulting, propanesulfonyl, isopropanolamine, butanesulfonyl, deformities.aromatherapy and triftormetilfullerenov; and examples of the lower alkylsulfonyl (which may be substituted by halogen atoms) include differencesolving and triftormetilfullerenov.

Examples of amino groups (which may be substituted WITH lower3-C6alkyl groups or cycloalkyl) include amino group, methylaminopropyl, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, dimethylaminopropyl, ethylpropylamine, cyclopropylamino, cyclopentylamine and cyclohexylamine.

Examples of the lower alkoxycarbonyl include methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl; examples of carbamoyl (which may be substituted by lower alkyl groups include N-methylcarbamoyl, N-ethylcarbazole, N-isopropylcarbamate and N,N-diethylcarbamoyl; and examples of aminomethylpropanol (which may be substituted by lower alkyl groups) include aminomethyl, N-methylaminomethyl, N-ethylaminomethyl, N-propylaminoethyl, N-isopropylaminomethyl, N-butylaminoethyl, N,N-dimethylaminomethyl and N,N-diethylaminomethyl.

Examples of acylaminoacyl include formulatingemedium, acetamidomethyl, propionylcarnitine, bucillamine, isobutylamine, benzylaminopurine and N-acetyl-N-isopropylaminomethyl; examples of N-alkoxycarbonylmethyl include methoxycarbonylaminophenyl, ethoxycarbonylmethyl, tert-butoxycarbonylmethyl and N-(tert-butoxycarbonyl)-N-isopropylaminomethyl; and primarity substituted by halogen atoms) include panelgroup, 2-pervenire, 3-pervenire, 4-pervenire, 2-chlorpheniram, 3-chlorpheniram, 4-chlorophenylurea, 2,4-dichlorphenol, 3,4-dichloroprop, 2,6-dichlorphenol, aftercrop and bifenilovye; and examples of heteroaryl include the group pyridine-2-yl group pyridin-4-yl group, pyridine-3-yl, 2-foilgroup, 3-foilgroup, 2-tailgroup, 3-tailgroup, honeygrove, intelligroup, benzofuranyl, bastianello, benzothiazolium, benzisoxazoles and benzisothiazolinone.

In practice examples R3in the group-N(R2)C(=O)R3imagine two groups, one of which is C1-C10alkyl group (which may be substituted by halogen atoms), preferably from C1to C8), including methylgroup, ethylpropyl, n-profilgruppen, isopropylate, tert-bodygraph, n-bodygraph, isobutylparaben, sec-bodygraph, n-intergruppo, 1-ethylpropyl, n-cellgroup, chlorotalpa, triptoreline, trichloromethylmercapto, 1-bromoisobutyrate, Hortiflorexpo and 1-chloromethyl-1-mutilating; and the other presented WITH a3-C8cycloalkylcarbonyl (preferably from C3to C6), including cyclopropylamino the p include vinylgroover, allgraph, businessgroup and extirpa; examples of C2-C4alcininku include ethnicgroup, properlyhow and businessgroup; examples of aracip include benzerrou, 2-venlateshappa; a lower alkyl group (substituted amino group include aminomethylpropanol and 1-aminoisobutyrate; an example of aracip (substituted amino group) is the group of 1-amino-2-phenylethyl, etc.; and examples of the lower alkyl groups substituted by allmineral) include acetamidomethyl and 1-acetylaminophenol.

An example of Uralkaliy (replaced by allmineral) is the group of 1-acetylamino-2-phenyl; examples of the lower alkyl groups substituted by alkoxycarbonylmethyl) include tert-butoxycarbonylamino and 1-(tert-butoxycarbonylamino)isobutyramide; and an example of Uralkaliy (replaced by alkoxycarbonylmethyl) is 1-(benzyloxycarbonylamino)-2-venlateshappa.

Examples of airgroup (which may be substituted by halogen atoms, lower alkyl groups (which may be substituted by halogen atoms), lower alkylthiol, an amino group, a nitro-group or cyano) include panelgroup, 2-pervenire, 3-ftormetilirovaniya, 2,6-dichlorphenol, 4-metilfenidato, 2-metilfenidato, 2,4-dimethylphenyl, 4-triptoreline, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylthiophenyl, 4-AMINOPHENYL, 4-acetylaminophenol, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 4-nitrophenylthio and afterglow.

Examples of heteroaryl include 2-foilgroup, 2-tailgroup, group, pyridine-4-yl group, pyridine-2-yl group, a thiazol-4-yl, group oxazol-4-yl group of the pyrazole-3-yl group, imidazol-4-yl group, isothiazol-5-yl, group isoxazol-5-yl, piratininga, group, pyrimidine-2-yl, group pyridazin-3-yl group (1,2,3-thiadiazole)-4-yl group (1,2,5-thiadiazole)-3-yl, furutani, group, benzothiazol-2-yl group, a benzimidazole-2-yl group, a quinoline-2-yl, group, isoquinoline-2-yl and the group cinoxacin-2-yl.

Examples of the lower alkoxygroup include a methoxy group, ethoxypropan, n-propoxylate, isopropoxy, butoxypropyl, tert-butoxypropan and 1-ethylpropoxy; examples3-C6cycloalkenyl include cyclopropylamino, cyclopentyloxy and cyclohexyloxy; and an example of alloctype is fenoxaprop. Replacement groups, which is Karami Het are With the group, such as the group, thiazol-2-yl (which may be substituted) and the group, thiazol-4-yl (which may be substituted). The most preferable examples are groups such as the group, thiazol-2-yl, group, thiazol-4-yl, group 2-aminothiazol-4-yl, group 2-allmynotes-4-yl, group 2-alkoxycarbonylmethyl-4-yl, group 2-alkoxyethanol-4-yl, group 2-alkylthiomethyl-4-yl, group 2-alkylsulfonates-4-yl, group 2-alkylsulfonates-4-yl, group 2-aridisol-4-yl and 2-bromothiazole-4-yl.

There are two rigid structure, i.e., form "E" and "Z" in oxomnik fragments oxime derivative represented by the General formulas (1) and (2). The rigid structure of both forms of "E" and "Z" is included in the scope of this invention. Typically synthesized products derived oxime include both forms in the form of mixtures, and can be distinguished by separation and purification.

Although the form "Z" of the derived oxime is more effective as a chemical for disease control plants than form "E", "Z" gradually changed to the form "E" under normal conditions, and the relationship between forms of "E" and "Z" will stabilize at a constant ratio. A constant ratio between forms of "E" and "Z" waruiru, which are represented by the General formulas (1) and (2) can be obtained, for example, in the following ways (a way to get And see the end of the description). However, it should be understood that the methods of obtaining the oxime derivative of the present invention is not limited to the methods described in the following examples of the preparation.

Derived oxime represented by the General chemical formula (1) or (2) is obtained by the following steps: receiving hydroxykynurenine (b) by reacting compounds of azole-methanone (a) with hydroxylamine, and interaction received hydroxykynurenine with halogenated compounds (C) or (d) in the presence of salts (such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine, N,N-dimethylaminopyridine). As a method for the synthesis of compounds azole-methanone apply the method described, for example, in "Synthesis", S. 976 (1982).

In practice, the chemical structure of the compounds represented by the General formulas (1) and (2) that is produced by these stages of receipt, provided in table 1-66.

Agricultural chemicals, especially agents for combating plant diseases, which contain derivatives of the research institutes of various diseases of plants, caused by bacteria and mold fungi, and is particularly effective when the plant diseases caused by mold fungi. Plant diseases caused by mold fungi, include a wide variety of types of plant diseases caused by Oomycetes (oomycetes), and diseases of plants caused by Pyricularia oryzae.

Agricultural agents of the present invention is particularly effective when such plant diseases like downy mildew and late blight Solanaceae or caused by Phytophthora rot of various plants, which include a large variety of plant diseases caused by oomycetes, such as Plasmopara viticola, Pseudoperonospora cubensis, Phytophthora melonis, Phytophthora capsici, Phytophthora infestans, Peronospora. brassicae, Peronospora. destructor, Peronospora. spinaciae and Peronospora. manshurica; and Peronospora. viciae, Phytophthora nicotianae var. nicotianae, Phytophthora infestans, Pseudoperonospora humuli,Phytophthora cinnamomi, Phytophthora capsici, Phytophthora fragariae, against damage of various agricultural products Pythium bacteria, Pythium aphanidermatum and Pyricularia oryzae.

Agricultural agents of this invention can be used as such or can usually be used in combination with known auxiliary substances such as solid and liquid carriers, dispersing agents, diluents, emulsifiers, chemicals, sposobstvuyuthie by selection of the formulation in the form of a wettable powder, solutions, oil solutions, powders, granules and drugs type of sols.

Examples of solid and liquid carriers include, for example, talc, clay, bentonite, kaolin, diatomite, montmorillonite, mica, vermiculite, gypsum, calcium carbonate, white carbon, wood powder, starch, alumina, silicate salt, polymer glycol, waxes, water, alcohols (such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol), petroleum fractions such as petroleum ether, kerosene, solvent-naphtha), aliphatic and alicyclic hydrocarbons (such as n-hexane, cyclohexane), aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene and methylnaphthalene), halogenated hydrocarbons (such as chloroform, dichloromethane), ethers (such as isopropyl simple ether, ethylene oxide and tetrahydrofuran), ketones (such as acetone, methyl ethyl ketone, cyclohexane and methyl isobutyl ketone), esters (such as ethyl acetate, butyl acetate, the acetate of ethylene glycol and amylacetate), acid amides (such as dimethylformamide and dimethylacetamide), the NITRILES (such as acetonitrile, propionitrile, Acrylonitrile), sulfoxidov (takii ethylene glycol).

Examples of excipients include, for example, surface-active agents non-ionic type (such as plain polyethylene alkilany ether complex alkilany ether of polyethylene oxide, a simple alkylphenolic ether of polyethylene oxide, polyoxyethylene arbitrarily ester and arbitrarily ester), surfactants of the anionic type (such as Las, alkylsulfonyl, alkylsulfate of polyethylene oxide and arylsulfonate), surfactants cationic type (such as alkylamines followed, polioksietilena and salts of Quaternary ammonium bases), amphoteric surfactants (such as acylaminoalkyl and alkyldiphenylamine), polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, gum Arabic, tragacanth gum, xanthan gum, polyvinyl acetate, gelatin, casein, and sodium alginate.

In addition, these agents can be used in combination with known agricultural chemicals, such as agricultural and horticultural fungicides, herbicides, plant growth regulators, insecticides, acaricides, and fertilizers. Although the content of these chemicals varies depending,5 to 95% by weight and preferably from 2 to 70% by mass.

Can be applied in various ways, including the application to the foliage (wetting foliage), drawing on the garden soil (soil treatment), drawing on the water surface (processing surface water) and applied to the seeds (seed treatment).

The amount of data of agricultural chemicals varies depending on the type of plants to which they are applied, and disease. When chemicals are applied to the foliage, then it is preferable to apply them using a liquid solution in the amount of 50-300 liters per 10 ar at a concentration of 1-10000 h/million, preferably 10-1000 h/million, as an effective chemical concentration. For application to the surface of the water or on the soil, it is preferable to use 0.1 to 100 g / 10 ar. When treated seeds, it is preferable to apply 0.001 to 50 g data agricultural agents per 1 kg of seeds.

Hereinafter the invention will be described in more detail with reference to the following examples of methods of preparation, sample composition and sample tests. It should be understood that the invention is not limited to the following examples.

Example obtain 1

Hydroxylamine hydrochloride (0.20 g, 2.82 mmol) and triethylamine (0.4 ml, 2.8 mmol) are added to races of the com within 48 hours. After concentrating the thus reacted solution to the residue add ethyl acetate, washed with water and the residue is dried with magnesium sulfate. The solvent is removed by distillation and the residue is purified column chromatography and obtain (Z)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime (0.16 g) and (E)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime (0.04 g).

(Z)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime: 1H-NMR (CDCl3): of 2.54 (s, 3H), 7,30~to 7.50 (m, 5H), 8,30~8,45 (Shir.d, 1H).

MS (m/e): 219 (M+).

(E)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime: 1H-NMR (CDCl3): of 2.54 (s, 3H), 7,35~of 7.60 (m, 5H), 8,00~8,20 (Shir.d, 1H).

MS (m/e): 219 (M+).

Example of getting 2

(Z)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime (9,31 g, 0.04 mol) is dissolved in acetonitrile (677 ml), add the hydrochloride of 2-picolylamine (the 10.40 g, 0.07 mol) and heated under reflux for 5 hours. After concentrating the thus reacted solution, the residue is extracted with ethyl acetate and extracted substance is dried after washing with water. The solvent is removed by distillation, the residue is purified column chromatography and obtain (Z)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-O-(2-feast of the J=7,6 Hz, 1H), 7,30~7,42 (m, 3H), 7,35 (d, J=7.8 Hz, 1H), 7,44~to 7.50 (m, 2H), TO 7.67 (J=7,8 Hz, J=7,6 Hz, 1H), 8,56 (d, J=4.9 Hz, 1H).

MS (m/e): 310 (M+).

Example of getting 3

(E)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-oxime (0,30 g, 1.4 mmol) dissolved in acetone (20 ml), add potassium carbonate (0.32 g, 2.0 mmol) and the hydrochloride of 2-picolylamine (0.34 g, 2.0 mmol) and heated under reflux for 3 days. After concentrating the thus reacted solution, the residue is extracted with ethyl acetate, and after washing with water, the residue is dried with magnesium sulfate. The solvent is removed by distillation, the residue is purified column chromatography and get (E)-(5-methyl-1,2,3-thiadiazole-4-yl)phenylmethanone-O-(2-pyridyl)methyl-oxime.

1H-NMR (CDCl3): at 2.59 (s, 3H), of 5.40 (s, 2H), 7,21 (DD, J=a 4.83 Hz, J= to 8.70 Hz, 1H), 7,31~7,72 (m, 7H), 8,58 (J=4,88 Hz, 1H).

MS (m/e): 310 (M+).

Example 4

Hydroxylamine hydrochloride (4,48 g, 63.1 mmol) and triethylamine (8,8 ml, 63.1 mmol) are added to a solution in ethanol (85 ml) (3-methyl-1,2,5-thiadiazole-4-yl)phenylmethanone (3,22 g, 15.7 mmol) and heated under reflux for 8 hours. Then the reacted solution is concentrated and to the residue is added ethyl acetate/water for extraction. The residue is dried with the indicate (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)-phenylmethanone-oxime (2,18 g).

1H-NMR (CDCl3): of 2.53 (s, 3H), 7,27~7,56 (m, 5H), charged 8.52~8,78 (Shir.d, 1H).

MS (m/e): 219 (M+).

Example of getting 5

60% sodium hydride (2,41 g, 60,0 mmol) are added to DMF (150 ml) (N, N-dimethylformamide) and cooled with ice and then add the (Z)-(3-methyl-1,2,5-thiadiazole-4-yl)phenylmethanone-oxime and stirred for 40 minutes. It reacted this way to the solution is added dropwise a solution in DMF (110 ml), 4-chloromethyl-2-isopropylimidazole (7,76 g of 35.6 mmol). After a gradual ascent of the reaction solution to room temperature it is stirred for 20 hours. The solvent of the reaction solution is removed under reduced pressure and to the residue is added ethyl acetate/water for extraction. Extracted solution was dried with magnesium sulfate after washing with water. The solvent is removed by distillation and the residue is purified column chromatography and obtain (Z)-(3-methyl-1,2,5-thiadiazole-4-yl)phenylmethane-O-(2-isopropylaminomethyl-4-yl)methyloxime.

1H-NMR (CDCl3): 1,22 (d, J=6,91 Hz, 6N), is 2.41 (s, 3H), 2,47~was 2.76 (m, 1H), total of 5.21 (s, 2H), 6.89 in (s, 1H), 7,28~of 7.60 (m, 5H), 9,50-9,90 (Shir.d, 1H).

MS (m/e): 401 (M+).

An example of obtaining 6

Solution in pyridine (55 ml) hydroxylamine hydrochloride (5, who receive 21 hours with stirring. Then the reacted solution was condensed, the residue is dissolved in ethyl acetate. After washing with diluted hydrochloride and subsequent washing with water, the residue is dried by magnesium carbonate. After removal of solvent and purification of the residue column chromatography

get (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-oxime (2,13 d) and (E)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-oxime (0,79 g).

(Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-oxime: 1H-NMR (CDCl3): of 2.38 (s, 3H), 7,30~a 7.62 (m, 2H), 7,89~8,00 (Shir.d, 1H).

MS (m/e): 219 (M+).

(E)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-oxime: 1H-NMR (CDCl3): to 2.55 (s, 3H), of 7.48~a 7.62 (m, 2H), 7,89~8,00 (Shir.d, 1H).

MS (m/e): 219 (M+).

Example of getting 7

60% sodium hydride (0,43 g, 10.6 mmol) are added to DMF (16 ml) and cooled with ice, and to this solution is added with stirring a solution in DMF (20 ml) of (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-oxime (0,94 g, 4,36 mmol). To the specified reacted solution was added a solution in DMF (15 ml) of 4-chloromethyl-2-triphenylimidazole (2,71 g, 6,94 mmol). After adjusting the reaction solution to room temperature, the reaction solution is stirred for 4 days. The solvent of p is the solvent removed by distillation, the residue is purified column chromatography and obtain (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-O-(2-triphenylimidazole-4-yl)methyloxime(0,59 g) (a Derivative of 9-(s)-6(Z)).

1H-NMR (CDCl3): of 2.23 (s, 3H), 5,11 (s, 2H), 6,27 (s, 1H), 6,80~6,97 (Shir.d, 1H), 7,13~of 7.60 (m, 20N).

MS (m/e): 557 (M+).

Example obtain 8

1M hydrochloride (0.6 ml) are added to a solution in acetone (15 ml) of (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-O-(2-triphenylimidazole-4-yl)methyloxime and heated for 8 hours under reflux. The solvent of the reaction solution is removed under reduced pressure and add a solution of ethyl acetate/saturated solution of acid sodium carbonate and extracted, then the solution is brought to pH=7. Extracted solution was washed with water and the residue is dried with magnesium sulfate. The solvent is removed by distillation and the residue is purified column chromatography and obtain (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-O-(2-aminothiazol-4-yl)methyloxime (0.05 g) (a Derivative of 8-(c)-1(Z)).

1H-NMR (CDCl3): 2,31 (s, 3H), 4,85~5,10 (Shir.d, 1H), 5,14 (s, 2H), 6,46 (s, 1H), 7,32~7,66 (m, 5H).

MS (m/e): 315 (M+).

Example of getting 9

Anhydride triperoxonane acid (7 ml) are added to (Z)-2 hours under stirring. The reaction solution is concentrated and the residue purified column chromatography and obtain (Z)-(3-methyl-1,2,5-oxadiazol-4-yl)phenylmethanone-O-(2-triftoratsetilatsetonom-4-yl)methyloxime (0,063 g) (a Derivative of 8-(C)-14(Z)).

1H-NMR (CDCl3): of 2.26 (s, 3H), of 5.26 (s, 2H), 7,07 (s, 1H), 7,28~7,56 (m, 5H), 7.68 per~8,10 (Shir.d, 1H).

MS (m/e): 411 (M+).

Physical and chemical data, such as range of1H-NMR and mass spectrum derived oxime, obtained in much the same way as those shown in the above examples, the receiving tables 67-81.

Next will be described examples of compiling agricultural agents using oxime derivative obtained according to this invention. If not indicated otherwise, the compounds are mixtures of forms a "Z" and "E".

Example composition 1: dust

2 parts by weight of oxime derivative of compounds from compound No. 1-(a)-1 through connection 66-(b)-10 is mixed with 98 parts by weight of clay and the mixture is pulverized to obtain a fine powder of dust.

Example composition 2: dispersible in water powder

20 parts by weight of oxime derivative of connections from the connection 1-(a)-1 through connection 66-(b)-10 is mixed with 68 parts by weight of clay, 8 parts is getting dispersible in water powder.

Example of compound 3: granules

5 parts by weight of oxime derivative of connections from the connection 1-(a)-1 through connection 66-(b)-10 is mixed with 90 parts by weight of a mixture of equivalent mass of bentonite and talc and 5 parts by weight of Las sodium and the mixture is crushed to form granules.

The effectiveness of the compounds obtained according to the invention against various plant diseases will be described hereinafter with reference to the following examples of tests. The status of the test plants when testing the effectiveness of suppression of diseases of these chemicals is determined by the degree of damage that appears on the foliage, or the number of plants affected Phytophthora observed visually, and the results were evaluated in four stages "a", "b", "C" and "D". Degree "And" choose, when there is no plant damage or not withered plants, and the degree of "In" is chosen when the number of diseased plants, which include plants with damaged or withered plants, approximately 10% of the total number of plants. Degree "C" is chosen when the number of diseased plants is about 25%, and the degree D is chosen when the number of diseased plants exceeds 50%.

The test example 1: Test for inhibition of disease plants, vyzyvaemsya water, containing surfactant (0,02%), so that the concentration of the effective component was 250 h/million thus Prepared solution spray on the foliage at the stage of 3-4 leaves of tomato (variety Toyofuku) grown in plastic pots with a diameter of 9 see After air drying them infect by spraying a dispersion of spores of Phytophthora infestans after incubation in a moist chamber at 20oWith in 24 hours disputes give rise at room temperature. After 5 days determine the degree of disease development. The test results against Phytophthora infestans on tomatoes is shown in table 82. As an agricultural chemical use comparison dispersible in water powder masaba in quantities 1250 h/million and 250 h/million

The test example 2: Test for inhibition of disease of plants caused by Pseudoperonospora cubensis

Dispersible in water, the powder obtained by the method shown in example composition 2, was diluted with water containing a surfactant (0,02%), so that the concentration of the effective component was 50 h/million thus Prepared solution spray on the foliage at stage 3 of the sheet of cucumber (variety: Tokiwa Shinchibai), which are grown plastma cubensis, after incubation in a moist chamber at 25oWith in 24 hours disputes give rise at room temperature. After 5 days determine the degree of disease development. The test results against Pseudoperonospora cubensis on cucumbers are shown in table 83. As an agricultural chemical use comparison dispersible in water powder masaba in quantities 1250 h/million and 50 h/million

Example test 3: Test for inhibition of disease of plants caused by Pseudoperonospora cubensis (test drive of the leaf)

From the first sheet of cucumber (variety: Tokiwa Shinchibai) at the stage of 2-3 leaves cut out the stamped disc with a diameter of 10 mm, Then the disk is immersed for 30 minutes in a solution of pharmaceutical chemical at a concentration of effective ingredient 10 h/million using dispersible in water powder prepared according to example composition 2. After air drying infect a drop of the dispersion of spores Pseudoperonospora cubensis (resistant to metalaxyl strain of fungi). Stand in a moist chamber, the bacteria are cultivated in the artificial climate (day - 14 hours; 25oDay, 18oWith the night) for 7 days and determine the degree of disease development. The results of these tests on the sheet against Pseudoperonospora cubensis shown in Tasca of masaba and metalaxyl.

Example test 4: Test for inhibition of disease of plants caused by Plasmopara viticola (the test drive of the leaf)

The disk sheet, carved stamp from a sheet of grapes (variety: neo masukatto) immersed for 30 min in containing the chemical solution, which is prepared using a dispersible powder in water at a concentration effective component 10 h/million After air drying infect a drop of the dispersion of spores of two fungi, consisting of (A) sensitive to metalaxyl Plasmopara viticola and (B) resistant to metalaxyl Plasmopara viticola, and cultivated mushrooms for 7 days in a humid chamber artificial climate. The results of these tests on the sheet against Plasmopara viticola shown in table 85.

Example test 5: Test for inhibition of disease of plants caused by Pythium aphanidermatum

A mixture of sterilized soil and Pythium aphanidermatum placed in a deep Petri dish with a diameter of 15 cm After planting 10 seeds of cucumber (variety: Nouryoku Shintokiwa) in each Cup, moisten the soil diluted with water dispersion of water-dispersible powder prepared according to example composition 2 at a concentration effective component 1000 h/million After wetting the Cup is placed in a humid chamber and in terms of installing artificial the s tested against Pythium aphanidermatum shown in table 86. Agricultural chemical comparison of this test is 1000 h/million water-dispersible powder Captan.

Example test 6: Test for inhibition of disease of plants caused by Pyricularia oryzae

Diluted water solution of water-dispersible powder prepared according to example composition 2 at a concentration effective component 250 h/million , sprayed on the leaves of rice plants (variety: Aichi Asahi) at the stage of 3-4 leaves, which are grown in a plastic pot with a diameter of 9 see After air drying infect spray dispersion dispute Pyricularia oryzae and after incubation in a moist chamber for 24 hours disease photosynthesis to occur in the greenhouse and the amount of disease determined after 7 days. The test results against Pyricularia oryzae shown in table 87. Agricultural chemical comparison of this test is 500 ppm water-dispersible powder phthalide.

In addition, the practical structure of the compounds of this invention are shown in tables 88-90, where Het, Het, X, Y and n are the same as defined in General formula (1) and (2), and Me denotes methylgroup.

Physical and chemical data, such as range of1H-NMR and mass spectrum are presented in tables 91-97.

In addition, examples of tests of pesticides according to this invention will be described next.

Example test 7: Test for inhibition of disease of plants caused by Pseudoperonospora cubensis

The test is carried out in the same way as shown in test example 2. The test results are shown in table 98.

Example test 8: Test for inhibition of disease of plants caused by Pseudoperonospora cubensis (test drive of the sheet).

The test is carried out in the same way as shown in test example 3. The test results are shown in table 99.

Example test 9: Test for inhibition of disease of plants caused by Plasmopara viticola (the test drive of the sheet).

The test is carried out in the same way as shown in test example 4. The test results are shown in table. 100.

Industrial applicability

This invention relates to novel oxime derivative, which does not cause chemical damage to plants and have sufficient effectiveness against various plant diseases, as well as to pesticides and tools for combating plant diseases, which contain such oxime derivatives as active ingredients.

Table (A)-(G) depict Mascitelli, used for the synthesis of these compounds, and in tables (C)-(G) presents the physico-chemical properties, which are characterized by a structural isomer (E/Z), the data of nuclear magnetic resonance and mass spectrometry of each connection.

In these tables, the following notation:

s - singlet,

d - doublet,

dd = doublet of doublet,

m - multiplet,

br broadened,

Hz - Hz,

ddd, doublet of doublet of doublet,

tt - triplet triplet.

1. Derived oxime of General formula (1)

< / BR>
where R1denotes a hydrogen atom or a lower alkyl group;

X is a halogen atom, a cyano, a nitro-group, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms) or phenyl group;

n = 0, 1, 2;

Het And denotes a 6-membered nitrogen-containing aromatic cyclic structure, which contains one or two nitrogen atom, including the pyridine ring which may be substituted by a halogen atom or a lower alkyl group, a pyrimidine ring, pyrazinone ring or benzododecinium with him nitrogen-containing aromatic cyclic structure, including quinoline - the volume of hydrogen, halogen atom or lower alkyl group which may be substituted by a halogen atom.

2. Oxime derivatives of under item 1, where Het And in the General formula (1) denotes pyridyloxy group which may be substituted by a halogen atom or a lower alkyl group.

3. Derived oxime of General formula (2)

< / BR>
where R1is a hydrogen atom;

X is halogen atom, cyano or lower alkyl group (which may be substituted by a halogen atom);

n = 0, 1, 2;

Het is the same as defined in chemical formula (1) where Y denotes a lower alkyl group;

Het With denotes a 5-membered nitrogen-containing aromatic structure or benzododecinium with it nitrogen-containing aromatic structure, which contains one or more nitrogen atoms, or which may contain a sulfur atom or an oxygen atom, including imidazole ring, thiazole ring, a pyrazol ring, 1,2,4-triazole ring, 1,2,4-thiadiazole ring, 1,2,3-thiadiazole ring, benzimidazole ring, benzothiazoline ring or imidazo[1,2-a] pyridine ring which may be substituted by one or two substituting groups, and groups which are able to replace the nitrogen atom indicated Inoi group, triphenylmethyl group and N, N-disubstituted sulfamoyl group (substituted lower alkyl group); and group, will be able to replace the carbon atom of the specified 5-membered nitrogen-containing aromatic cyclic structures, are groups selected from a halogen atom, a C1-C6alkyl group (which may be substituted by halogen atom), C1-C5alkoxygroup (which may be substituted by halogen atom), lower allylthiourea (which may be substituted by halogen atom), lower alkylsulfonyl (which may be substituted by halogen atom), lower alkylsulfonyl (which may be substituted by halogen atom), amino group (which may be substituted by a lower alkyl group), lower alkoxycarbonyl, carbamoyl group (which may be substituted by lower alkyl groups), pyridine-4-ilen group, an amino group which may be substituted triphenylmethyl group, N-(alkoxycarbonyl)(alkyl)aminomethyl group, alkylthiomethyl group or carbamoyl group which may be substituted by lower alkyl groups, and groups of formula-N(R2)C(= O)R3in which R2denotes a hydrogen atom or methylgroup, and R3-8cycloalkyl, a lower alkyl group (substituted amino group), a benzyl group, a lower alkyl group (substituted alkoxycarbonylmethyl), phenyl group (which may be substituted by halogen atom, lower alkoxygroup or cyano), 2-thienyl group or a lower alkoxygroup.

4. Derived oxime under item 3, where Het With in the General formula (2) represented by the following formula:

< / BR>
where R4denotes a hydrogen atom, an amino group, a C1-C5alkoxygroup (which may be substituted by halogen atoms), lower allylthiourea (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms), lower alkylsulfonyl (which may be substituted by halogen atoms) or a group represented by the formula-NHC(= O)R3in which R3denotes a hydrogen atom, a C1-C10alkyl group (which may be substituted by halogen atoms), C3-C8cycloalkyl, benzyl group, lower alkyl group, a substituted amino group, a lower alkyl group substituted by alkoxycarbonylmethyl, phenyl group (which may be substituted by halogen atoms, NISS is alkoxygroup;

R5is a hydrogen atom or a halogen atom.

5. Derived oxime under item 4, where R4refers to a group represented by the formula-NHC(= O)R3in which R3denotes a hydrogen atom, a C1-C6alkyl group (which may be substituted by halogen atom), WITH3-C6cycloalkyl group, phenyl group (which may be substituted by halogen atoms, lower alkoxycarbonyl or cyano groups), a 2-thienyl group or a lower alkoxygroup, R5- the hydrogen atom.

6. Means for combating plant diseases containing as an active ingredient derived oxime according to any one of paragraphs. 1-5.

7. Means on p. 6 for combating plant diseases, effective against plant diseases caused by fungi.

8. The method of obtaining hydroxykynurenine following General formula (b):

< / BR>
where X, n and Het B are as hereinafter defined for the General formula (a),

including the stage of interaction derived isomethadone represented by the General formula (a),

< / BR>
with hydroxylamine,

where X denotes a halogen atom, a cyano, a nitro-group, a lower alkyl group (which may be the replacement of the foam;

n = 0, 1, 2;

Het - oxime derivatives of the cyclic structure represented by the following formula:

< / BR>
< / BR>
< / BR>
where Y denotes a lower alkyl group.

9. The method of obtaining the derivative of the oxime, the General formula (1) of the General formula (1):

< / BR>
where Het B, X and n are as defined for the following General formula (b);

Het and R1are as defined for the following General formula (C);

or the General formula (2)

< / BR>
where Het, X and n are as defined for the following General formula (b);

Het and R1are as defined for the following General formula (d),

including the stage of interaction of hydroxykynurenine represented by the following General formula (b) with a halogen compound represented by the following General formula (C) or (d), in the presence of base

General formula (b):

< / BR>
where X denotes a halogen atom, a cyano, a nitro-group, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms) or phenyl group;

n = 0-2;

Het - oxime derivatives of cyclic p is ogena or a lower alkyl group, which may be substituted by a halogen atom;

General formula (C):

< / BR>
where R1denotes a hydrogen atom or a lower alkyl group;

Het And matter specified in paragraph 1; and

Z is a chlorine atom, a bromine atom or an iodine atom;

General formula (d):

< / BR>
where R1denotes a hydrogen atom or a lower alkyl group;

Het With a matter specified in paragraph 3. ;

Z is a chlorine atom, a bromine atom or an iodine atom.

10. Hydroxykynurenine General formula (b)

< / BR>
where X denotes a halogen atom, a cyano, a nitro-group, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms) or phenyl group;

n = 0, 1, 2,

Het B - oxime derivatives of a cyclic structure, which is expressed by the following formula:

< / BR>
< / BR>
< / BR>
where Y is a lower alkyl group.

11. Hydroxykynurenine under item 10, where in the General formula (b) X denotes a halogen atom, a lower alkyl group (which may be substituted by halogen atoms), lower alkoxygroup (which may be substituted by halogen atoms) or phenyl group and n = 0-2.

12. Hydroxykynurenine under item 10, where in the General formula is rosediana by p. 10, where in the General formula (b) n= 0 and Y in In Het denotes a methyl group.

 

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The invention relates to new derivatives of kalaidjieva, fungicides, method of combating fungal diseases of crops and intermediate compounds for obtaining

The invention relates to new derivatives of piperidine-ketocarboxylic acids of the formula (I), where R1- COR4or SO2R4, R4means of alkenyl, substituted phenyl or pyridine, naphthyl, honokalani, chinoline, benzothiophene, dihydroxyphenyl or pyridyl, substituted with allmineral, R2- C1-C6-alkyl which can be substituted by phenyl or pyridium, R3group-OR6or other6where R6means hydrogen, C1-C6-alkyl, which may be a phenyl, pyridine or morpholinium, their tautomeric and isomeric forms, and salts

The invention relates to new derivatives of benzoxazinone General formula (I), where R1means N or carboxyethyl, R2represents hydrogen or alkyl, and R3is a different derivatively of amino acids, dipeptides and hydrazones acid groups, respectively, their conjugates with active substances, such as residues from a number of penicillin

The invention relates to compounds: N-[[2'-[[(4,5-dimethyl-3-isoxazolyl)amino] sulfonyl] -4-(2-oxazolyl)[1,1'-biphenyl] -2-yl] methyl]-N,3,3-trimethylbutyramide and N-(4,5-dimethyl-3-isoxazolyl)-2'-[(3,3-dimethyl-2-oxo-1-pyrrolidinyl)methyl] -4'-(2-oxazolyl)[1,1'-biphenyl] -2-sulfonamide and their pharmaceutically acceptable salts, such as lithium, sodium or potassium salt or a salt with a base, which is an organic amine

The invention relates to new derivatives of oxadiazole General formula I, in which X and Y denote oxygen or nitrogen, and X and Y cannot both be oxygen or nitrogen; Z denotes a radical of the formula II, R1means phenyl radical, which is optionally substituted directly or through alkylene bridges with the number of carbon atoms from 1 to 4 once, twice or three times by one or more substituents from the series halogen, C1-C4-alkyl, CF3, -NR5R6, NO2, -OR7

The invention relates to compounds of formula (I) R4-A-CH(R3)N(R2)B-R1where a is optionally substituted phenyl group, provided that the group-CH(R3)N(R2)B-R1and-OR4are in the 1,2-position relative to each other on the carbon atoms of the ring, and provided that the atom of the ring, in anthopology towards OR4- joined the group (and therefore in the 3-position relative to the-CHR3NR2-linking group) is unsubstituted; In - pyridyl or pyridazinyl; R1located on the ring In the 1,3 - or 1,4-position relative to the-CH(R3)N(R2)-linking group and represents carboxy, carbarnoyl or tetrazolyl, or R1represents a group of formula СОNRaRa1where Rais hydrogen or C1-6alkyl, and Ra1- C1-6alkyl, or R1represents a group of formula CONHSO2Rbwhere Rb- C1-6alkyl, trifluoromethyl, or a 5-membered heteroaryl selected from isooxazolyl and thiadiazolyl, optionally substituted C1-6the alkyl or C1-4alkanolamines; R2- C1-6alkyl; R3is hydrogen; R4- C1-4alkyl, C3-7cycloalkyl,1-3alkyl or their pharmaceutically acceptable salt or in vivo hydrolyzable esters

The invention relates to a new method of obtaining isoxazolidinone the compounds of formula (II) in which R represents an optionally substituted aromatic hydrocarbon group or its salt, by reacting the compounds of formula (1) or its salt with the compound of the formula (2) in the presence of an inorganic base in an aqueous solvent with getting aspartates the compounds of formula (3), which interacts with acetic anhydride using dimethylaminopyridine as a catalyst in the presence of base followed by heating for decarboxylation to obtain the compounds of formula (4), to which is added p-toluensulfonate acid to obtain oxazolidinedione derivative of the formula (5)which then restores the tetrahydrofuran in the presence of NaBH4and methanol to obtain oxazolidinones the compounds of formula (6) and its further interaction with methylchloride in the presence of triethylamine to obtain methanesulfonate derivative of the formula (7), which interacts with the compound of the formula (8) in the presence of potassium carbonate to obtain benzylidene derivative of the formula (9), which is further restored in an atmosphere of hydrogen for the floor is warping with obtaining the compounds of formula (11)

The invention relates to new compounds of the formula (I) or their salts, where X, Y independently is hydrogen, halogen; Z is oxygen; Q is chosen among the Q1-Q9described in the claims and containing heterocycles with nitrogen, and sulfur; Ar is pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl, isothiazole or phenyl, or pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl, isothiazole or phenyl substituted with up to five substituents, when Q - Q3or Q6substituted phenyl is excluded

The invention relates to new bicyclic to carboxamide formula (i) in which (1) X represents N and (a) Z is =CR1-CR2and Y is N, Z is =CR1and Y represents O, S or NR4or (C) Z is = CR1-N= and Y represents CR2or (2), X represents NR4Z represents CR1= and Y is N, Q is O, R1and R2are СОR6, C(= NOR6R13, alkyl-C(=NOR6R13, NR8R9, CF3or R6, R3is1-6alkoxygroup, R4represents H or alkyl, R5is heteroaryl, optionally substituted with halogen, alkyl, CONR11R12, CF3or CN, aryl, substituted with halogen; R6represents H, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, arylalkyl, heteroaromatic or heteroseksualci, R7represents alkyl, hydroxy, OR10, NR8R9CN, CO2H, CO2R10, CONR11R12, R8and R9represent H or alkyl, or NR8R9represents a heterocyclic ring, optionally substituted by R14, R10represents an alkyl, heterocycle, R11and R12represent H or alkyl, and the salts

The invention relates to therapeutic active usacycling or azabicyclic compounds, method of their preparation and to pharmaceutical compositions comprising these compounds
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