Methods and intermediates for obtaining methylamino-methoxykynuramine acids

 

(57) Abstract:

The invention relates to a method of producing methylamino - methoxykynuramine acids of the formula I, where Y represents a C-organic radical through reaction of Pinner interaction achilleid formula II with an alcohol and subsequent interaction of the formed in the Pinner reaction of ester of the formula (IV) with hydroxylamine to obtain the oxime of the formula V by methylation of the oxime of the formula V to oximoula ether of the formula VI or b) somethingitaliano obtaining oximoula ester of formula VI, followed by interaction oximoula ester of formula VI with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III R-OH, boiling point above 75C. the Technical result is to simplify the process and obtaining the pure target product with high yield. 3 S. and 7 C.p. f-crystals, 23 PL.

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The invention relates to a method of producing methylamino-methoxykynuramine acids of the formula I

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in which Y represents C-organic radical,

through the reaction of Pinner interaction achilleid formula II

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with alcohol and later the m receiving oxime of the formula V

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methylation of the oxime of the formula V to oximoula ether of the formula VI

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or

b) with O-methylhydroxylamine obtaining oximoula ether of the formula VI

and the subsequent interaction oximoula ester of formula VI with methylamine.

From existing publications there are various ways of getting methylamino - methoxykynuramine acids. However, these methods are either very time consuming, as a result of the implementation of many stages, and/or do not provide a satisfactory yield of the final product, or require the use of expensive or, in the case of application methods on an industrial scale associated with large practical difficulties of reagents (see European application EP-A 398692, EP-A 463488, EP-A 477631, EP-A 579124, EP-A 582925, EP-A 585751, EP-A 617011, EP-A 617014, international application WO-A 92/13830, WO-A 93/07116, WO-A 93/08180, WO-A 94/08948, WO-A 94/11334, WO-A 94/14322, WO-A 94/14761, WO-A 94/19331, WO-A 94/22812, the Japan patent JP-A 04/182461, JP-A 05/201946, JP-A 05/255012, Germany application DE 4410424.3 and DE 4421182.1).

In addition, the publications known through the reaction of Pinner interaction lanceton formula II with methanol and subsequent conversion into the corresponding methyl esters - methoxykynuramine acids of the formula I' (see evropeycami is also the formation of significant amounts of esters of benzoic acid, katalevich esters and amides.

Secondly, this known method has the following disadvantage: if you want to get particularly preferred compounds of formula IIA' (means chloromethyl)

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for example, by the methods described in the claims of Germany DE-A 4223382 and DE-A 4311722, and then the interaction with methanol to transform into a complex ketoesters of the formula X

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the formation of compounds X with a high degree of purity is difficult. The reason for this is due to the fact that the physical properties of ketoesters of formula X is formed during the first two reactions (according to the orders of Germany DE-A 4223382 and DE-A 4311722) associated by-products (primarily substituted phthalide and substituted 2-chlorodibenzofuran) are very similar, resulting in purification, for example by distillation, if at all feasible, can be carried out only with great difficulty and considerable expense.

Accordingly, the application produced using known methods ketoesters leads to the formation of contaminated derivative products, which only with great difficult to clean.

In accordance with this invention was based on the task razrabotat acids, which would require expensive and hazardous reagents and which, moreover, would obtain the desired intermediate and final products with high degree of purity.

Based on this, a method was found of obtaining methylamino - methoxykynuramine acids of the formula I

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in which Y represents C-organic radical through reaction of Pinner interaction achilleid formula II

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with alcohol and the subsequent interaction of the formed in the Pinner reaction of ester of the formula IV

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a) with hydroxylamine to obtain the oxime of the formula V

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methylation of the oxime of the formula V to oximoula ether of the formula VI

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or b) with O-methylhydroxylamine obtaining oximoula ether of the formula VI

and the subsequent interaction oximoula ester of formula VI with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III

R-OH (III),

boiling point which is above the 75oC.

The proposed method is based on the principle that due to the application in response Pinner high-boiling alcohols are formed - ketoesters, which are also volatile ingredients. Consequently uvelichiyovaetsja the possibility of separation by distillation. When using high-boiling alcohols, in addition, reduces the quantity of generated by-products, which allows more selective and the best way to get the desired product.

In the process according to the invention are mainly so that in a mixture of alcohol, acid, and optionally an inert solvent, at temperatures in the range -10oC to 150oC, preferably from 20oC to 130oC, primarily from the 50oC to 110oC, enter the additives of achilleid formula II.

For use in the method according to the invention are suitable in principle are all spirits having a boiling point of which at normal pressure is above the 75oC, preferably above 90oC, especially above 120oC. Examples of such alcohols are ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, Isobutanol, tert-butanol, n-pentanol and its isomers, n-hexanol and its isomers, heptanol, octanol, nonanol or decanol and related isomers, halogenated alcohols, such as 2-chloroethanol, 3-chloropropanol, 4-chlorobutanol, 5-chloropentane, 6-chlorohexanol, 7-chloroheptane, 8-chlorooctane or 9-chlorononane and related isomers, and alkoxyalkanols, takecontrol, 5-ethoxyethanol, 6-methoxyamino, 6-etoxisclerol, 7-methoxyethanol, 7-ethoxyethanol, 8-methoxyethanol, 8-ethoxyethanol, 9-methoxyethanol or 9-toxinogenic and corresponding isomers.

Particularly preferred is ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2,2-dimethyl-1-propanol, 1-methyl-2-butanol, 2-methyl-1-butanol, 3 - methyl-2-butanol, 1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 3 - octanol, 1-heptanol, 1-octanol and 2-chloroethanol. The most preferred n-pentanol.

The amount used alcohol for the method according to the invention is not crucial, as a rule, use 1-10 moles of the compounds of formula III, preferably 1-5 moles, especially 1-3 mol per mole of applied achilleid formula II. Alcohol can also serve as a solvent. In this case, use an excess of at least 20 moles, preferably at least 10 moles, especially at least 5 moles per mole of achilleid formula II.

The acid can be applied to all suitable for use according to the publications in the Pinner reaction of inorganic or organic acids. The preferred application of N. the slots, such as hydrochloric and Hydrobromic acid).

Acid is used usually in an excessive amount of from 1 to 5 moles, preferably 2-5 mol, especially of 2.5-3.5 mole per mole of achilleid formula II.

As inert solvents suitable aprotic polar or non-polar organic solvents, particularly hydrocarbons (e.g. pentane, hexane, cyclohexane, petroleum ether), aromatic solvents (e.g. benzene, toluene, o-, m - or p-xylene, chlorobenzene, nitrobenzene and anisole), halogenated hydrocarbons (e.g. dichloromethane, trichloromethane, carbon tetrachloride and 2,2'-dichloroethane) and ethers (e.g. diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, tetrahydropyran, dioxane or anisole), or mixtures of these solvents.

Preferably the Pinner reaction is carried out in the presence of water, and is usually used amount of from 0.5 to 1.5 mol of water per mol of achilleid.

The amount of inert solvent for the method according to the invention is not crucial. As a rule, can be used from 2 wt.% up to 40 wt.% solvent in terms of the number of achilleid formula II.

who authorized the mixture. High or low blood pressure is also valid, but it does not provide any additional benefits.

The reaction mixture is processed by conventional techniques, e.g. by mixing with water, separating the phases and, if necessary, by chromatographic purification of the crude products. Intermediate and final products are obtained partly in the form of colorless or slightly colored in brown viscous oil, which under reduced pressure and moderately elevated temperatures to remove volatile components, or which is subjected to cleaning (if necessary by pre-distillation). If the intermediate and final products are obtained as solids, purification can also be carried out by recrystallization or extraction from the solution.

Necessary to implement the exchange reaction aciklandi formula II can be obtained, for example, by means described in the claims of Germany DE-A 4223382, DE-A 4311722 and in European applications EP-A 493711, EP-A 564984 methods from the corresponding falicov. These publications are given in the present description by reference.

The formation of complex katalevich esters of the formula IV"

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in the method according to the invention to nastukov will still take place, these by-products will not be nonetheless an obstacle to the further application of ketoesters of formula IV in the synthesis of compounds of formula I, as during the subsequent reaction, they will be subject to splitting and transformation. If necessary dialkylamino ketocarboxylic esters of the acids of formula IV and in acidic conditions, for example, the introduction of hydrogen chloride in the presence of an inert solvent, could be translated into ketoesters of formula IV.

Further, when carrying out the reaction of the Pinner can form the corresponding amides - ketocarboxylic acids of the formula IV'. If the formation of amides - ketocarboxylic acids of the formula IV' is undesirable, the crude mixture of products that are suitable to re-subjected to the Pinner reaction, namely, if necessary several times, making amides - ketocarboxylic acids of the formula IV' will be transferred to the ketoesters of formula IV. By-products of the formula IV' in the method according to the invention are formed in much smaller quantities than in the known methods.

Alcoholysis of amides - ketocarboxylic acids of the formula IV' could be on a separate stage of the method, e.g. the, such as toluene, halogenated hydrocarbons such as dichloromethane, trichloromethane or carbon tetrachloride, or a simple ester, such as diethyl ether, diethylene glycol, tetrahydrofuran or dioxane. As acids can be used, for example, mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, carboxylic acids such as acetic acid or triperoxonane acid, or sulfonic acids such as p-toluensulfonate acid. Preferred among these acid - sulfuric acid, primarily in the form of a concentrated aqueous solution, and hydrochloric acid, which is most preferable to apply in gaseous form.

Receipt of joksimovich esters of the formula VI can be made based on ketoesters of the formula IV or amides - ketocarboxylic acids of the formula IV', the interaction with O-methylhydroxylamine or one of its acid-additive products. In addition, for use for the purposes described above is also suitable mixture of these compounds as starting materials, the mixture of crude products obtained in the reaction of Pinner, without further purification may also be used in later stages.

item deprotonirovannoi connection can be liberated from its salt by the addition of a strong base. As salts of O-methylhydroxylamine can be considered salt from one - to trekhosnovnykh acids, such as hydrochloric acid and sulfuric acid.

Preferably the use of an acid additive salts.

Typically, the reaction is carried out in the presence of a solvent or diluent. Suitable for this purpose solvents are predominantly aromatic hydrocarbons such as benzene, toluene, ortho-, meta - and paraxylene, chlorinated hydrocarbons such as methylene chloride, alcohols such as methanol, ethanol, n-propanol, n-pentanol, n-butanol, 3-methyl-1-butanol, n-hexanol, and ethers, such as dioxane, tetrahydrofuran and diethyl ether. Particularly preferred among the above mentioned methanol, ethanol or n-pentanol.

The proportion of doctow are not decisive; if not it is recommended to use an excess of one or another component that is equal to, for example, 10 mol.%, the parent compound should be used in stoichiometric quantities.

The reaction temperature is usually in the range from 0 to 100oC, preferably from 20 to 80oC.

In the case of the use of amides of the formula IV' as doctow reaction price what is that obtained by the reaction of Pinner mixture of raw foods without allocation of the total reaction mixture is subjected to interaction with O-methylhydroxylamine or one of its acid additive salts.

An alternative to this you can also ketoesters of formula IV, or amides - ketocarboxylic acids of the formula IV' or mixture of compounds of formulas IV and IV' expose to interact with hydroxylamine or one of its acid-additive products, to deliver the oxime of the formula V, and then to the latter optionally in the presence of a base and suitable solvent to introduce additives meteorologi agent.

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Hydroxylamine is used either in the form of an acid additive salt or in the form of free base, and deprotonirovannoi connection can be liberated from its salt by the addition of a strong base. As salts of hydroxylamines can be considered salt from one - to trekhosnovnykh acids, such as hydrochloric acid and sulfuric acid.

Preferably the use of an acid additive salts.

Typically, the reaction is carried out in the presence of a solvent or diluent. Suitable for this purpose solvents are the data hydrocarbons, such as methylene chloride, alcohols such as methanol, ethanol, n-propanol, n-pentanol, n-butanol, 3-methyl-1-butanol, n-hexanol. Particularly preferred among the above mentioned methanol, ethanol or n-pentanol.

The quantitative proportions of the starting products are not decisive; if not it is recommended to use an excess of one or another component that is equal to, for example, 10 mol.%, the parent compound should be used in stoichiometric quantities.

The reaction temperature is usually in the range from 0 to 100oC, preferably from 20 to 80oC. In the case of the use of amides of the formula IV' as doctow reaction should be carried out in the presence of an alcohol R-OH.

One variant of the method is that obtained in the reaction of Pinner mixture of raw foods without allocation of the total reaction mixture is subjected to interaction with hydroxylamine or one of its acid-additive products.

Methylation is carried out, for example, so that the oximes of the formula V in the presence of a diluent interaction with the ground is transferred to the corresponding salt, and then this latter is subjected to interaction with meteorous agent. When atestino be used in subsequent stages.

Among the preferred bases include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium methylate, sodium ethylate, n-pantilat sodium and tert-butyl potassium.

As agents of methylation suitable methylglucamide, especially methyl chloride, or dimethylsulfate.

As diluents for the reaction of formation of the oxime, and methylation can be used solvents such as, for example, acetone, dioxane, tetrahydrofuran, alcohols, such as methanol, ethanol, n-propanol, n-pentanol; sulfoxidov, such as dimethylsulfoxide, diethylsulfoxide, dimethyl sulfone, diethylsulfate, methylethylketon, tetramethylsilane; NITRILES, such as acetonitrile, benzonitrile, butyronitrile, isobutyronitrile, m-chlorobenzonitrile; N,N-disubstituted carbonamide, such as dimethylformamide, tetramethylrhodamine, N, N-dimethylbenzamide, N,N-dimethylacetamide, N,N-dimethylphenylacetate, amide N,N-dimethylcyclohexylamine acid amide and N,N-dimethylpropionic acid and homologous piperidine carboxylic acid, morpholin carboxylic acid, pyrrolidin carboxylic acid; the corresponding N, N-diethyl, N,N-dipropylamine, N,N-diisopropyl, N,N-diisobutylamine, N, is, N-methylformamide, N-ethylpyrrolidin, N-butylformamide, N-ethylpiperidine(6), N-organic; triamide hexamethylphosphoric acid; and appropriate mixtures. Preferred of them are dimethylacetamide, N-organic, dimethylformamide, dimethylsulfoxide and tetramethylarsonium. Particularly preferred N-organic and dimethylformamide.

Translation Asimov formula V in their anions and subsequent methylation is carried out, as a rule, at temperatures in the range from -20 to 100oC, preferably from 0 to 80oC, especially from 20 to 80oC.

The oxime of the formula V, the base and the alkylating agent is used in stoichiometric amount or use an excess of base and alkylating agent, comprising of 1.05 to 1.5 mol of alkylating agent and 1-1 .5 mole of base per mole of the oxime of formula V.

One of the variants of the method lies in the fact that the salt of the oxime without separation of the diluent used in the subsequent stages.

Joksimovi esters of the formula VI receive, usually in the form of mixtures of isomers, and Akimova bond (C=NOCH3) is represented partially in the E-configuration, and partially in the Z-configuration. Rearrangement of joksimovich esters in the E-configuration is hardly a catalyst, preferably the acid.

Suitable for the above purposes solvents are preferably acetone, aromatic hydrocarbons such as benzene, toluene, ortho-, meta-and paraxylene, chlorinated hydrocarbons such as methylene chloride, alcohols such as methanol, ethanol, n-propanol, n-butanol, n-pentanol, 3-methyl-1-butanol and n-hexanol; ethers, such as diethyl ether, dioxane, tetrahydrofuran, tert-butyl methyl ether and diisopropyl ether, sulfoxidov, such as dimethylsulfoxide, diethylsulfoxide, dimethyl sulfone, diethylsulfate, methylethylketon, tetramethylsilane; NITRILES, such as acetonitrile, benzonitrile, butyronitrile, isobutyronitrile, m-chlorobenzonitrile; N, N-disubstituted carbonamide, such as dimethylformamide, tetramethylrhodamine, N,N - dimethylbenzamide, N,N-dimethylacetamide, N,N-dimethylphenylacetate, amide N, N-dimethylcyclohexylamine acid amide and N,N-dimethylpropionic acid and homologous piperidyl carboxylic acid, morpholin carboxylic acid, pyrrolidin carboxylic acid; the corresponding N,N-diethyl, N,N-dipropylamine, N,N-diisopropyl, N,N-diisobutylamine, N,N-dibenzylamine, N,N-diphenyl, N-methyl-N-phenyl, N-cyclohexyl-N-methyl, N-ethyl-N-t is oligon; triamide hexamethylphosphoric acid; and appropriate mixtures thereof, and also mixtures thereof with water. Particularly preferred of them are methanol, ethanol, n-pentanol, toluene and diethyl ether.

As acceptable acids primarily mineral acid, for example, Perlina acid, sulfuric acid, phosphoric acid, halogen acids such as hydrochloric acid, aliphatic sulfonic acids, such as triftormetilfullerenov acid, aromatic sulfonic acids such as p-toluensulfonate acid, and halogenated alcancarao acid, such as triperoxonane acid. The most preferred hydrogen chloride.

The acid used is usually 0.01 to 10 times, especially 0.01 to 5-fold molar amount relative to the amount of the isomeric mixture of compounds of formula VI.

Temperature range isomerization is generally in the range from -20 to 100oC, preferably from 0 to 80oC.

For rearrangement of joksimovich esters takes some time depending on temperature and primarily on the amount of acid is approximately 1-90 hours, preferably 2-10 hours

To get the one to first concentrate or further dilute. The preferred option is that obtained after the formation of joksimovich esters a solution of crude product, however without further concentration or dilution directly treated with acid.

Thus obtained Joksimovi esters of formula VI may then interact with methylamine to transfer to methylamide --methoxykynuramine acids of the formula I

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The exchange reaction carried out by well-known methods in an inert organic solvent at temperatures in the range of 0oC to 100oC, preferably between 10oC to 70oC.

As solvents are used primarily acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, n-pentanol, N-organic, dimethylformamide, dimethylacetamide and dimethylsulfoxide.

Methylamine are usually used in excess, and methylamine or injected into a gas in the reaction mixture or the reaction mixture is mixed with aqueous or alcoholic solution of methylamine.

In the case when the amides of formula I in the process of obtaining a formed in the form of mixtures of isomers with respect to the double bond in the group C=NOCH3they can, if necessary with the aid of the s E-isomers.

The proposed method is suitable, in addition, to obtain methyl esters --methoxykynuramine acids of the formula I'

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when Joksimovi esters of the formula VI praeteritorum by well-known methods (see Houben-Weyl, volume E5, pages 702-707; Tetrahedron 42, 6719 (1986)). The transesterification is carried out in generally the following manner.

The crude product is dissolved in an excessive amount of methanol, and then by well-known methods or the addition of mineral acids or the addition of bases (for example, methanolate sodium) is subjected to interesterification.

The proposed method is suitable forth primarily for methylamino --methoxykynuramine acids of the formula IA

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in which the substituents and the index have the following meanings:

R1means hydrogen, hydroxy, mercapto, cyano, nitro, halogen, optionally substituted alkylsulfonyl, optionally substituted, alkylsulfonate, optionally substituted cycloalkyl, optionally substituted, aryloxy, optionally substituted arylsulfonyl, optionally substituted, arylsulfonyl, optionally substituted heterocyclyl or optionally substituted, getariako,

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Rameans cyano, nitro, halogen, C
m denotes 0 or an integer in the range from 1 to 4, and the radicals Racan be different, if m>1;

Rbmeans hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, quinil, heterocyclyl, alkylaryl, cycloalkylcarbonyl, alkenylboronic, alkynylaryl, heterocalixarenes, alkoxycarbonyl, aryl, hetaryl, arylcarbamoyl, heterylcarbonyl, arylsulfonyl, geturiresolver or group C(R')=NOR";

R' means hydrogen, hydroxy, cyano, nitro, amino, halogen, optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkenyl, alkenylacyl, alkanity, alkenylamine, quinil, alkyloxy, alkylthio, alkylamino, cycloalkyl, cycloalkene, cycloalkylation, cyclooctylamine, cycloalkenyl, cycloalkenyl, cycloalkenyl, cyclooctylamine, heterocyclyl, heterocyclic, heterocyclic, heterocyclisation, aryl, aryloxy, aaltio, arylamino, heteroaryl, heteroaromatic, heteroaromatic or heteroarenes;

R means hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, quinil, heterocyclyl, aryl or heteroaryl,

Rcrepresents a group specified for Rbor hydroxy, cyano, nitro, amino, guarraci, getarity or hetarylamino;

or Rband Rcboth together with the C atom to which they are linked, represent a carbocyclic or heterocyclic ring.

Compounds of this type are known from the above publications as active ingredients designed to combat malicious mushrooms.

The proposed method is suitable, in addition, to obtain methyl esters --methoxykynuramine acids of formula I-A

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in which the substituents and the index have the values specified above for the decryption of the compounds of formula IA. Such compounds are known, for example, from European application EP-A 253213, EP-A 254426, EP-A 363818, EP-A 378308, EP-A 385224, EP-A 386561, EP-A 400417, EP-A 407873, EP-A 460575, EP-A 463488, EP-A 472300, international application WO-A 94/00436 and Germany application DE 4421180.5, for combating harmful fungi.

In accordance with this particularly preferred as starting materials are compounds of the formula IIA

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To get known from publications of active substances does not play a significant role, do as compounds of formula IIA are those substances in which R1means hydrogen, hydroxy, mercapto, cyano, nitro, optionally substituted cargo>1represents an optionally substituted alkylsulfonyl, optionally substituted cycloalkyl, optionally substituted, aryloxy, optionally substituted arylsulfonyl, optionally substituted heterocyclyl or optionally substituted, getariako, hydroxyphthalimide radical

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or oximino radical

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Specified in the first group, the radicals R1preferably at stages IV and V and above all at stages VI and I to the methods described in the above publications can be transferred to the deputies of the second group. The relevant data of the above publications included in the present description as a reference.

When the decoding of the symbols in the above formulas are General concepts adopted to denote the following substituents:

halogen means fluorine, chlorine, bromine and iodine;

alkyl means saturated, remotemachine or branched hydrocarbon radicals with 1 to 4, 6 or 10 carbon atoms, for example C1-C6alkyl, like methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2 is methylbutyl, 2.2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

alkylsulphonyl means remotemachine or branched alkyl group with 1-10 carbon atoms (as specified above), linked via a carbonyl group (-CO-) to the skeleton;

alkylsulfonate means remotemachine or branched alkyl group with 1-10 carbon atoms (as mentioned above), are related through sulfonyloxy (SO2-O-) to the skeleton;

halogenated means remotemachine or branched alkyl group with 1-4 carbon atoms (as specified above), and in these groups, partially or totally, the hydrogen atoms may be replaced by halogen atoms as mentioned above; for example, C1-C2halogenated as chloromethyl, dichloromethyl, trichloromethyl, vermeil, deformity, trifluoromethyl, CHLOROFORMATES, dichloromethyl, chlorodifluoromethyl, 1-foretel, 2-foretel, 2,2-dottorati, 2,2,2-triptorelin, 2-chloro-2-foretel, 2-chloro-2,2-dottorati, 2,2-dichloro-2-foretel, 2,2,2-trichlorethyl and pentafluoroethyl;

alkoxy means remotemachine or branched alkyl group with 1-4 or 10 carbon atoms (as specified above), swaye alkoxygroup with 1-10 carbon atoms (as defined above), linked via a carbonyl group (-CO-) to the skeleton;

halogenoalkane means remotemachine or branched halogenoalkane group with 1-4 carbon atoms (as specified above), linked through an oxygen atom (-CO-) to the skeleton;

alkylthio means remotemachine or branched alkyl group with 1-10 carbon atoms (as specified above), linked through a sulfur atom (-S-) to the skeleton;

alkylamino means remotemachine or branched alkyl group with 1-4 carbon atoms (as specified above), connected via the amino group (-NH-) to the skeleton;

dialkylamino means independent from each other remotemachine or branched alkyl group with 1-4 carbon atoms (as specified above), linked through a nitrogen atom (-N-) to the skeleton;

alkenyl means unsaturated, remotemachine or branched hydrocarbon radicals with 2 to 10 carbon atoms and a double bond in any position, for example, C2-C6alkenyl as ethynyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, the Il-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4 - pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

alkenylacyl means unsaturated, remotemachine or branched hydrocarbon group with 2 or 3-6 or 10 carbon atoms and a double bond in any position (as mentioned above), linked through an oxygen atom (-O-) to the skeleton;

alkanity means unsaturated, remotemachine or razvetvlenno), linked through a sulfur atom (-S-) to the skeleton;

alkenylamine means unsaturated, remotemachine or branched hydrocarbon group with 2 or 3-6 or 10 carbon atoms and a double bond in any position (as mentioned above), connected via the amino group (-NH-) to the skeleton;

alkenylboronic means unsaturated, remotemachine or branched hydrocarbon group with 2-10 carbon atoms and a double bond in any position (as mentioned above), linked via a carbonyl group (-CO-) to the skeleton;

quinil means remotemachine or branched hydrocarbon group with 2-10 carbon atoms and a triple bond in any position, for example, C2-C6quinil as ethinyl, 1-PROPYNYL, 2-PROPYNYL, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-PROPYNYL, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 1-methyl-3-butynyl, 2-methyl-3-butenyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-PROPYNYL, 1-ethyl-2-PROPYNYL, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 3-methyl-1-pentenyl, 3-methyl-4-pentenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 1,1-dimethyl-2-butinyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethylaminoethoxy means remotemachine or branched hydrocarbon group with 2 or 3-6 or 10 carbon atoms and a triple bond in any position (as mentioned above), linked through an oxygen atom (-O-) to the skeleton;

alkylthio means remotemachine or branched hydrocarbon group with 2 or 3-6 or 10 carbon atoms and a triple bond in any position (as mentioned above), linked through a sulfur atom (-S-) to the skeleton;

alkynylamino means remotemachine or branched hydrocarbon group with 2 or 3-6 or 10 carbon atoms and a triple bond in any position (as mentioned above), connected via the amino group (-NH-) to the skeleton;

alkenylboronic means remotemachine or branched hydrocarbon group with 2-10 carbon atoms and a triple bond in any position (as mentioned above), linked via a carbonyl group (-CO-) to the skeleton;

cycloalkyl means a monocyclic alkyl group with 3-12 carbon members of the cycle, for example, C3-C8cycloalkyl as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

cycloalkane means a monocyclic alkyl group with 3-6, 8, or 12 carbon members of the cycle (as described above), linked through an oxygen atom (-O-) to the skeleton;

cycloalkyl means a monocyclic alkyl group with 3-6, 8, or 12 carbon members of the cycle (as described above), C3-6, 8 or 12 carbon members of the cycle (as described above), linked through the amino group (-NH-) to the skeleton;

cycloalkylcarbonyl means a monocyclic alkyl group with 3-6, 8, or 12 carbon members of the cycle (as described above), linked via a carbonyl group (-CO-) to the skeleton;

cycloalkenyl means monocyclic hydrocarbons with 5 to 12 carbon members of the cycle and one or two double bonds in the cycle, such as C3-C8cycloalkenyl as cyclopropyl, cyclobutyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctyl and cyclohexadienyl;

cycloalkenyl means monocyclic alkenylphenol group with 5 to 8 or 12 carbon members of the cycle and one or two double bonds (as defined above), linked through an oxygen atom (-O-) to the skeleton;

cycloalkenyl means monocyclic alkenylphenol group with 5 to 8 or 12 carbon members of the cycle and one or two double bonds (as defined above), linked through a sulfur atom (-S-) to the skeleton;

cyclooctylamino means monocyclic alkenylphenol group with 3 to 8 or 12 carbon members of the cycle and one or two double bonds (as defined above), linked through the amino group (-NH-) to the skeleton;

heterocyclyl osasto members cycle heteroatoms from the group including oxygen, sulfur and nitrogen, for example, 5-or 6-membered heterocycles (heterocyclyl), containing, along with the carbon members of the cycle from one to three nitrogen atoms and/or one oxygen atom or sulfur, or one or two oxygen atom and/or sulfur, two atoms of oxygen and/or sulfur, such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrofuryl, 3-tetrahydrofuryl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinone, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolinones, 4-isothiazolinone, 5-isothiazolinones, 3-pyrazolidone, 4-pyrazolidone, 5-pyrazolidone, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-diazolidinyl, 4-thiazolidine, 5-thiazolidine, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidine-3-yl, 1,2,4-oxadiazolidine-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-thiazolidin-3-yl, 1,3,4-oxadiazolidine-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-thiazolidin-2-yl, 2,3-dihydrofuro-2-yl, 2,3-dihydrofuro-3-yl, 2,4-dihydrofuro-2-yl, 2,4-dihydrofuro-3-yl, 2,3-dihydrothieno-2-yl, 2,3-dihydrothieno-3-yl, 2,4-dehydration-2-yl, 2,4-dehydration-3-yl, 2,3-pyrrolin-2-yl, 2,3-pyrrolin-3-yl, 2,4-pyrrolin-2-yl, 2,4-pyrrolin-3-yl, 2,3-isoxazolin-3-yl, 3,4-isoxazolin-3-yl, 4,5-isoxazolin-3-yl, 2,3-isoxazolin-4-yl, 3,4-isoxazolin-4-yl, 4,5-isoxazolin-4-yl, 2,3-isoxazolin-4-yl, 3,4-isothiazolin-4-yl, 4,5-isothiazolin-4-yl, 2,3-isothiazolin-5-yl, 3,4-isothiazolin-5-yl, 4,5-isothiazolin-5-yl, 2,3-dihydropyrazol-1 - yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol - 1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazolo-2-yl, 2,3-dihydrooxazolo-3-yl, 2,3-dihydrooxazolo - 4-yl, 2,3-dihydrooxazolo-5-yl, 3,4-dihydrooxazolo-2-yl, 3,4-dihydrooxazolo-3-yl, 3,4-dihydrooxazolo-4-yl, 3,4-dihydrooxazolo - 5-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1,3-dioxane-5 - yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrofuranyl, 3-tetrahydropyridine, 4-tetrahydropyridine, 2-tetrahydropyrimidines, 4-tetrahydropyrimidine, 5-tetrahydropyrimidine, 2-tetrahydropyranyl, 1,3,5-tetrahydropyrazin-2-yl and 1,2,4-tetrahydropyrazin-3-yl, particularly preferred 1-pyrrolidinyl, 1-pyrazolidine, 1-imidazolidinyl, 2-isoxazolidine, 3-oxazolidinyl, 2-isothiazolinones, 3-thiazolidine, 2,3-dihydropyrrol-1-yl, 2,5-dihydropyrrol-1-yl, 2,3-dihydropyrazol-1-yl, 4,5-dihydropyrazol-1-yl, 2,3-dihydroimidazole-1-yl, 4,5-dihydroimidazole-1-yl, 2,3-dihydroisoxazole-2-yl, 2,3-dihyd is heterocyclics means a saturated or partially unsaturated cyclic radical, containing besides carbon atoms as members of the cycle heteroatoms from the group comprising oxygen, sulfur or nitrogen (as indicated above), linked through an oxygen atom (-O-) to the skeleton;

heterocyclic means a saturated or partially unsaturated cyclic radical containing besides carbon atoms as members of the cycle heteroatoms from the group comprising oxygen, sulfur or nitrogen (as indicated above), linked through a sulfur atom (-S-) to the skeleton;

heterocyclisation means a saturated or partially unsaturated cyclic radical containing besides carbon atoms as members of the cycle heteroatoms from the group comprising oxygen, sulfur or nitrogen (as indicated above), linked through the amino group (-NH-) to the skeleton:

aryl, respectively aryloxy, aaltio, arylamino, arylcarbamoyl, arylsulfonyl, arylsulfonyl means an aromatic mono - or polycyclic hydrocarbon radicals, directly associated with the skeleton, or, respectively, (aryloxy) through an oxygen atom (-O-), (arieti) via a sulfur atom (-S-), (arylamino) through the amino group (-NH-), (arylcarbamoyl) via a carbonyl group (-CO-), (arylsulfonyl) through sulfonyloxy group (-SO2-) and (arylsulfonate, naphthyloxy, phenanthridinone and the corresponding thio-, carbonyl, sulfonylurea and sulfonylacetanilide;

hetaryl, respectively getariako, getarity, hetarylamino, heterylcarbonyl and getresolver means an aromatic mono - or polycyclic radicals which, together with the carbon members of the cycle (s) can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen atom or sulfur or one oxygen atom or one sulfur atom and which are directly linked to the skeleton, or, respectively, (retailexe) through an oxygen atom (-O-), (getarity) via a sulfur atom (-S-), (hetarylamino) through the amino group (-NH-), (heterylcarbonyl) via a carbonyl group (-CO-) and (getresolver) through sulfonyloxy group (-SO2), for example,

is a 5-membered heteroaryl containing one to three nitrogen atoms: 5-cyclic heteroaryl group which, together with the carbon atoms may contain as members of the cycle from one to three nitrogen atoms, for example 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazole-3-yl and 1,3,4-triazole-2-yl;

is a 5-membered heteroaryl containing from one to four Ath a sulfur atom: 5-cyclic heteroaryl group, which, together with the carbon atoms may contain as members of the cycle from one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen or one oxygen atom or one sulfur atom, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazole, 4-isothiazole, 5-isothiazole, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazole-3-yl, 1,2,4-thiadiazole-5-yl, 1,2,4-triazole-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazole-2-yl, 1,3,4-triazole-2-yl;

- condensed 5-membered heteroaryl containing from one to four nitrogen atoms or one to three nitrogen atoms and/or one oxygen atom or one sulfur atom: 5-cyclic heteroaryl group which, together with the carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur atom or oxygen or one oxygen atom or one sulfur atom as members of the cycle and in which two adjacent carbon member or nitric member and the adjacent carbon member can be connected bridge connection, abrasonis, isobenzofuranyl, indolyl, isoindolyl, benzisoxazole, benzoxazole, benzothiazole, benzothiazolyl, indazoles, benzimidazoles, pyrrolopyridine, pyrrolopyrimidine, pyrrolopyrimidine, pyrrolopyrazine, pyrrolotriazine, properidine, properidine, propertymodel, foroperational, fenotiazinas, thienopyridines, thienopyridines, thienopyrimidine, thienopyridine, teentiatans, imidazopyridines, imidazopyridines, imidazopyridines, imidazopyridines, imidazolidinyl, pyrazolopyrimidines, pyrazolopyrimidines, pyrazolopyrimidine, pyrazolopyrimidines, pyrazoloacridine, isoxazolidine, isoxazolidine, isoxazolidine, isoxazolidine, isoxazolidine, oxazolopyridine, oxazolopyridine, oxazolopyridine, oxazolopyridine, oxazolidinyl, isothiazolinones, isothiazolinones, isothiazolinones, isothiazolinones, isothiazolinones, triazolopyridines, triazolopyridazines, triazolopyrimidine, triazolopyridines, diazolidinyl, triazolopyridines, triazolopyridazines, triazolopyrimidine, triazolopyridines and triazolopyridazines;

bound through the nitrogen of the 5-membered heteroaryl containing from one to four nitrogen atoms, the TA: 5-cyclic heteroaryl group, which, together with the carbon atoms may contain as members of the cycle from one to four nitrogen atoms, respectively, from one to three nitrogen atoms and in which two adjacent carbon member or nitric member and the adjacent carbon member can be connected bridge connection buta-1,3-Dien-1,4-Delovoy group, and these cycles are connected to the skeleton via one of the nitrogen of the members of the cycle, such as 1-pyrrolyl, 1-imidazolyl, 1-pyrazolyl and 1,2,4-triazole-1 - yl;

to 6-membered heteroaryl containing from one to three, respectively, from one to four nitrogen atoms: 6-cyclic heteroaryl group which, together with the carbon atoms may contain as members of the cycle from one to three, respectively, from one to four nitrogen atoms, for example 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine-2-yl, 1,2,4-triazine-3-yl and 1,2,4,5-tetrazine-3-yl;

- condensed 6-membered heteroaryl containing from one to four nitrogen atoms: 6-cyclic heteroaryl group in which two adjacent carbon member can be connected bridge connection, forming an aromatic or heteroaromatic bi - or politics, for example x is performance communications group.

The definition of "optionally substituted(e)" with respect to alkyl, alkylcarboxylic, alkylsulfonyl, alkoxy, alkoxycarbonyl, alkylthio, alkylamino, dialkylamino-, alkenyl, alkenylacyl, alkanity, alkynylamino-, alkenylboronic, alkynylaryl, alkyloxy, alkylthio, alkylamino and alkylcarboxylic groups should be understood so that these groups can be partially or completely galogenirovannyie and/or may carry one to three radicals, preferably one, of the following: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiazolyl, halogen, C1-C6alkoxy, C1-C6halogenoalkane, C1-C6alkoxycarbonyl, C3-C6cycloalkyl, C1-C6alkylamino (NH group bearing an alkyl group, as defined above), di-C1-C6alkylamino (amino group carrying two independent from each other alkyl groups, as defined above), aryl, aryloxy, hetaryl or getariako, aaltio or getarity, with the latter representing aromatic, respectively heteroaromatic groups, in turn may be partially or fully galogenirovannyie and/or may bear from odnos1-C4alkyl, C1-C4halogenated, C1-C4alkoxy, C1-C4halogenoalkane, C1-C4alkylthio, C1-C4alkylamino, di-C1-C4alkylamino and C1-C4alkoxycarbonyl.

The definition of "optionally substituted(e)" to cycloalkenyl, cycloalkenyl, heterocyclyl, aryl and heterelmis groups (respectively corresponding hydroxy-, thio-, carbonyl, sulfonylurea and sulfonyloxy) should be understood so that these groups can be partially or completely galogenirovannyie and/or may bear from one to four radicals, preferably one or two, of the following: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiazolyl, halogen, C1-C6alkyl, C1-C6halogenated, C1-C6alkylsulphonyl, C1-C6alkoxy, C1-C6halogenoalkane, C1-C6alkoxycarbonyl, C1-C6alkylthio, C3-C6cycloalkyl,

C1-C6alkylamino (NH group bearing an alkyl group, as defined above) di-C1-C6alkylamino (amino group carrying two independent from each other alkyl groups as described above), Calkyl, aryloxyalkyl, aryloxy, hetaryl, getariako or 1-(C1-C6alkoxyimino)-C1-C6alkyl, and aromatic, respectively heteroaromatic groups can be partially or completely galogenirovannyie and/or to carry one to three groups selected from among the following: cyano, nitro, hydroxy, amino, carboxyl, aminocarbonyl, aminothiazolyl, C1-C4alkyl, C1-C4halogenated, C1-C4alkylsulphonyl, C1-C4alkoxy, C1-C4halogenoalkane, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylamino and di-C2-C4alkylamino.

The term "partially or fully halogenated(f)" means that in the described thus groups the hydrogen atoms associated with the C-atoms can be partially or completely be replaced by identical or different halogen atoms as mentioned above, especially fluorine atoms, chlorine and/or bromine.

Especially important are the intermediate products of formula IVA, IV'A, VA and VIA, in which R1represents a hydroxyl group.

Particularly preferred intermediates are those of the formulae IVA, IV'A, VA and VIA in konocti get active substances, described in the above publications.

Some of the particularly preferred intermediates are presented in the following tables.

Table 1

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is CH2CH2CH3and R1means connecting respectively one of the groups is presented in table A.

Table 2

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is (CH2)3CH3and R1means connecting respectively one of the groups is presented in table A.

Table 3

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is CH2CH(CH3)2and R1means connecting respectively one of the groups is presented in table A.

Table 4

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is CH(CH3)CH2CH3and R1means connecting respectively one of the groups is presented in table A.

Table 5

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is (CH2)4
Table 6

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is CH2CH2CH(CH3)2and R1means connecting respectively one of the groups is presented in table A.

Table 7

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is CH2C(CH3)3and R1means connecting respectively one of the groups is presented in table A.

Table 8

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is C(CH3)2CH2CH3and R1means connecting respectively one of the groups is presented in table A.

Table 9

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R denotes a Penta-2-yl, and R1means connecting respectively one of the groups is presented in table A.

Table 10

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R denotes a Penta-3-yl and R1means connecting respectively one of the groups is presented in table A.

Table 11

Compounds of formula IVA, VA and VIA, where Xnis undertaken in table A.

Table 12

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is 3-methylbut-2-yl, and R1means connecting respectively one of the groups is presented in table A.

Table 13

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is (CH2)5CH3and R1means connecting respectively one of the groups is presented in table A.

Table 14

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is 2-ethylhex-1-yl, and R1means connecting respectively one of the groups is presented in table A.

Table 15

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is (CH2)6CH3and R1means connecting respectively one of the groups is presented in table A.

Table 16

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is (CH2)7CH3and R1means connecting respectively one of the groups is presented in table A.

Table 17

Compounds of formula IVA, VA and VIA, where Xnis special in table A.

Table 18

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is 2-atexit-1-yl, and R1means connecting respectively one of the groups is presented in table A.

Table 19

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is 2-floret-1-yl, and R1means connecting respectively one of the groups is presented in table A.

Table 20

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is ethyl and R1means connecting respectively one of the groups is presented in table A.

Table 21

Compounds of formula IVA, VA and VIA, where Xnrepresents hydrogen, R is 1-methylethyl and R1means connecting respectively one of the groups is presented in table A.

Table 22

The compounds of formula IV'A, in which Xnrepresents hydrogen and R1means connecting respectively one of the groups is presented in table A.

Examples

Example 1

n-Pentalogy ester 2-(chloromethyl)phenylglyoxylic acid

< / BR>
18 g pentanol-1 (0,2 mol) dissolved 1.8 g of water and 80 g of toluene. ZAT is (and 0.09 mole) of 2-(chloromethyl)benzylcyanide. At room temperature and left for 2 hours for mixing and heated to 60oC and kept at this temperature for 8 hours Then the reaction mixture is allowed to cool, extracted once with 50 ml of 15% hydrochloric acid and three times with 50 ml of water, then concentrated to dryness.

Yield: 23 g (95% contain a 4.9% pentalofos ester of 2-(chloromethyl)benzoic acid).

A small amount purified by rapid chromatography on silica gel 60, for example, cyclohexane-toluene in the ratio of 2:1.

Large quantities purify by distillation.

1H-NMR (CDCl3) = 0,92 (t, 3H); of 1.28 to 1.48 (m, 4H); 1,67-of 1.84 (m, 2H); 4,39 (t, 2H); to 5.03 (s, 2H); 7,45 for 7.78 (m, 4H) ppm million

Example 2

(2-ethyl)hexyl ester of 2-(chloromethyl)phenylglyoxylic acid

< / BR>
30 g of 2-ethylhexanol (to 0.23 mole) is dissolved with 2.0 g of water and 80 g of toluene. At a temperature of 0-5oC bubbled through a solution of 14.6 g (0.4 mole) of hydrogen chloride, and then at 0oC is added dropwise 18 g of 2-(chloromethyl)benzylcyanide dissolved in 25 g of toluene. Then the reaction mixture for 2 hours and heated under stirring to 60oC. After exposure for 8 h at this temperature, allowed to cool to room temperature and once washed with 50 ml of 15m hold fast chromatography with cyclohexane-toluene in the ratio of 3:1 on silica gel 60.

Yield: 23 g (75%, purity >99%).

Example 3

n-Pentalogy ether 2-methoxyimino-2-[(2'-chloromethyl)phenyl] acetic acid

To a solution of 27 g (0.1 mole) of n-pentalofos ester of 2-(chloromethyl)phenyl-Glyoxylic acid in 50 ml of methanol was added 33 g (0.4 mole) of O-methylhydroxylamine, hydrochloride and 10 g of molecular sieve (3 ) in the form of dry granules and left for 16 h at room temperature. After filtering off the molecular sieve, the solution was concentrated, the residue was distributed between methyl tert-butyl ether and water, the organic phase is washed with water, dried over sodium sulfate and concentrated. As a result received 30 g (100%) of the compound indicated in the title, in the form of a light yellow oil, presented in the form of a mixture of E/Z-isomers (1:1). Separation of the isomers can be performed by column chromatography on silica gel (methyl tert-butyl ether-n-hexane).

E-isomer: colorless oil

1H-NMR (CDCl3): = of 0.87 (t, 3H); of 1.20 to 1.37 (m, 4H); 1,62-of 1.74 (m, 2H); of 4.05 (s, 3H); 4,27 (t, 2H); of 4.44 (s, 2H); 7,16 (dd, 1H); 7,32-7,51 (m, 3H) ppm million

Z-isomer: colorless oil

1H-NMR (CDCl3): = 0,89 (t, 3H); 1,24-of 1.41 (m, 4H); from 1.66-1.77 in (m, 2H); Android 4.04 (s, 3H); 4,30 (t, 2H); 4,88 (s, 2H); 7,32-7,47 (m, 3H); 7,58 (d, 1H) ppm million

Example 4

n-Pentile the RA 2 methoxyimino-2-[(2'-chloromethyl)phenyl] acetic acid (E:Z=1:1) in 500 ml of diethyl ether saturated with ice cooling hydrogen chloride. Then the reaction mixture was allowed to warm to room temperature and left at this temperature for mixing for 16 hours After concentration and purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 24,3 g (yield 81%) of the desired compound indicated in the title, in the form of a colorless oil.

1H-NMR: see example 1 (E-isomer).

Example 5

n-Pentalogy ether (E,E)-2-methoxyimino-2-{[2'-(1"-(4"'- chlorophenyl)-1"-methyl)aminoacetyl]phenyl}acetic acid

0.27 g (11 mmol) of sodium hydride were placed in 50 ml of dimethylformamide. Then portions were added 1.7 g of 4-chloroacetophenone and was stirred for 30 min at room temperature. Then was added dropwise 3.0 g (10 mmol) of n-pentalofos ether (E)-2-methoxyimino-2-[(2'-chloromethyl)phenyl] acetic acid in 10 ml of dimethylformamide and left for 2 h stirring at room temperature. The mixture was poured into cold 2M hydrochloric acid and was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over Na2SO4and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexa>): = 0,84 (t, 3H); 1,16-of 1.36 (m, 4H); 1,53-1,72 (m, 2H); to 2.18 (s, 3H); was 4.02 (s, 3H); 4,19 (t, 2H); 5,12 (s, 2H); 7,17-to 7.59 (m, 8H) ppm million

Example 6

Monomethylated (E, E)-2-methoxyimino-2-{ [2'-(1"-(4"'-chlorophenyl)-1"-methyl)aminoacetyl] phenyl}acetic acid

2.0 g (4.6 mmole) of n-pentalofos ether (E,E)-2-methoxyimino-2-{[2'-(1"-(4"'-chlorophenyl)-1"-methyl) aminoacetyl] phenyl} acetic acid was dissolved in 50 ml of tetrahydrofuran, mixed with 20 ml of 40% aqueous solution monomethylamine and was stirred for 3 h at room temperature. Then mixed with water and was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. The way it was obtained 1.6 g (92%) of the compound indicated in the title, in the form of a white powder with a melting point 117-119oC.

1H-NMR (CDCl3): = 2,17 (s, 3H); of 2.86 (d, 3H); of 3.94 (s, 3H); 5,11 (s, 2H); 6,72 (s, W, 1H); 7,19-of 7.55 (m, 8H) ppm million

Example 7

Monomethylated (Z)-2-methoxyimino-2-{[2'-(E)-(1"-(4"'-chlorophenyl)-1"-methyl) aminoacetyl]phenyl}acetic acid

0.09 g (3.7 mmole) of sodium hydride were placed in 10 ml of dimethylformamide. Then portions were added of 0.58 g of 4-chloroacetophenone and was stirred for 30 min at room temperature. Later on the ka of dimethylformamide, left for 30 min at room temperature for mixing, mixed with 10 ml of tetrahydrofuran and 10 ml of 40% aqueous solution monomethylamine and left to stir for 16 h at room temperature. After mixing with water, was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 1.0 g (yield 79%) indicated in the title compound in the form of a powder beige color with a melting point 111-113oC.

1H-NMR (CDCl3): = of 2.23 (s, 3H); 2,80 (d, 3H); Android 4.04 (s, 3H); of 5.39 (s, 2H); of 6.68 (s, W, 1H); 7,30-of 7.55 (m, 8H) ppm million

Example 8

Monomethylated (E, E)-2-methoxyimino-2-{ [2'-(1"-(4"'-chlorophenyl)-1"-methyl)aminoacetyl] phenyl}acetic acid

To a solution of 8.4 g (0,022 mol) of monomethylamine (Z)-2-methoxyimino-2-{ [2'-(E)-(1"-(4"'-chlorophenyl)-1"-methyl) aminoacetyl] phenyl} acetic acid in 300 ml of toluene was added 50 ml of a saturated ethereal solution of hydrogen chloride and left for 4 h at room temperature. After adding methyl tert-butyl ether was washed sequentially with saturated solution of NaHCO3. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained of 5.4 g (yield 65%) indicated in the title compounds as colorless crystals with a melting point 117-119oC.

1H-NMR (CDCl3: = 2,17 (s, 3H); of 2.86 (d, 3H); of 3.94 (s, 3H); 5,11 (s, 2H); of 6.71 (s, W, 1H); 7,19-of 7.55 (m, 8H) ppm million

Example 9

Amide 2-(chloromethyl)phenylglyoxylic acid

Of 16.5 g (92 mmole) of 2-(chloromethyl)benzylcyanide, 150 ml of concentrated hydrochloric acid and 150 ml of saturated ethereal solution of hydrogen chloride to prepare the mixture was stirred for 5 h at room temperature. Then was poured into water, the organic phase was separated, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) received a 13.4 g (yield 74%) indicated in the title compound in the form of a powder beige color with a melting point 105-107oC.

1H-NMR (CDCl3): = 4,90 (s, 2H); 5,79 (s, W, 1H); 7.03 is (s, W, 1H); 7,46-of 7.69 (m, 3H); 8,02 (d, 1H) ppm million

Example 10

n-Pentalogy EPE is emali in 200 ml of n-pentanol. Then barbotirovany hydrogen chloride until saturation, and the temperature was raised to 80oC. Then continued stirring for another 3 h Then the reaction mixture was concentrated, the residue was mixed with water and was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 1.1 g (yield 54%) indicated in the title compounds as colorless oils.

1H-NMR (CDCl3): = 0,92 (t, 3H); of 1.28 to 1.48 (m, 4H); 1,67-of 1.84 (m, 2H); 4,39 (t, 2H); to 5.03 (s, 2H); 7,45 for 7.78 (m, 4H) ppm million

Example 11

Monomethylated (E, E, E)-2-[[[[2-(methoxyimino)-1,2-(dimethyl)ethylidene] amino] oxy]methyl] -- methoxykynuramine acid

1.4 g (10 mmol) of potassium carbonate and 0.7 g (5.4 mmol) of (E,E)-2-hydroxyimino-3-methoxyaminomethyl were placed in 15 ml of dimethylformamide and stirred for 1 h at 50oC. Then was added 1.5 g (5.0 mmol) of n-pentalofos ether (E)-2-methoxyimino-2-[(2-chloromethyl)phenyl]acetic acid, dissolved in 5 ml of dimethylformamide, and stirred a total of 48 h at room temperature. It was further added 20 ml of 40% n the tion. After mixing with water, was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 1.5 g (yield 91%) indicated in the title compound as a white powder with a melting point of 67-69oC.

1H-NMR (CDCl3): = 1,95 (s, 3H); to 1.98 (s, 3H); 2,90 (d, 3H); to 3.92 (s, 3H); of 3.94 (s, 3H); of 5.05 (s, 2H); 6,70 (s, W, 1H); 7,13 was 7.45 (m, 4H) frequent. /million

Example 12

Monomethylated (E,E,E)-2-[[[[2-(methoxyimino)-1-(methyl)-2-(phenyl)ethylidene] amino]oxy]methyl] -- methoxykynuramine acid

2.2 g (16 mmol) of potassium carbonate and 0.65 g (3.4 mmole) of (E,E)-1-phenyl-1-methoxyimino-2-on-2-oxime was placed in 30 ml of dimethylformamide and stirred for 1 h at 60oC. 3 Quiroga was added 1.0 g (3.4 mmole) of n-pentalofos ether (E)-2-methoxyimino-2-[(2-chloromethyl)phenyl] acetic acid dissolved in 20 ml of dimethylformamide, and stirred first for 28 h at room temperature, and then for 17 hours at 60oC. After cooling, was added 50 ml of tetrahydrofuran and 15 ml of 40% aqueous solution monomethylamine and left for subsequent mixing n the major organic phase was washed with water, was dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 1.0 g (75% yield) specified in the title compound as a white powder with a melting point 127-130oC.

1H-NMR (CDCl3): = 2,10 (s, 3H); 2,84 (d, 3H); a 3.87 (s, 3H); to 3.89 (s, 3H); 4,91 (s, 2H); 6,62 (s, W, 1H); 7,12-7,33 (m, 9H) ppm million

Example 13

n-Pentalogy ether (E)-2-[[[1-phenyl-1,2,4-triazole - 3-yl] oxy]methyl]---methoxykynuramine acid

0,80 g (5.0 mmol) 3-hydroxy-1-phenyl-1,2,4-triazole and 3.5 g (25 mmol) of potassium carbonate were placed in 40 ml of dimethylformamide and within 10 minutes was stirred at room temperature. 3 Quiroga was added 1.5 g (5.0 mmol) of n-pentalofos ether (E)-2-methoxyimino-2-[(2-chloromethyl) phenyl] acetic acid, dissolved in 10 ml of dimethylformamide, and a small (on the tip of a spatula) quantity of potassium iodide and heated for 6 h to 100oC. After dilution with water, was extracted with methyl tert-butyl ether. The combined organic phases are washed with water, dried over sodium sulfate and concentrated. After purification by column chromatography on silica gel (methyl tert-butyl ether-n-hexane) was obtained 1.7 g (Wi-1,32 (m, 4H); 1.60-to 1,71 (m, 2H); Android 4.04 (s, 3H); to 4.23 (t, 2H); of 5.26 (s, 2H); 7,17-of 7.70 (m, 9H); of 8.25 (s, 1H) ppm million

Example 14

Monoethylamine (E)-2-[[[1-phenyl-1,2,4-triazole-3-yl] oxy] methyl] --methoxykynuramine acid

1.5 g (3.6 mmole) pentalofos ester from example 13 was dissolved in 50 ml of tetrahydrofuran, mixed with 10 ml of 40% aqueous solution monomethylamine and for 16 h and was stirred at room temperature. Then mixed with water, was extracted with methyl tert-butyl ether, the organic phase is washed with water, dried over sodium sulfate and centrifuged. The result was obtained 1.1 g (yield 86%) indicated in the title compound as a yellow oil.

1H-NMR (CDCl3): = 2,90 (d, 3H): 3,96 (s, 3H); and 5.30 (s, 2H): 6.87 in (s, W, 1H); 7,25-to 7.68 (m, 9H); 8,21 (s, 1H) ppm million

1. The method of producing methylamino-methoxykynuramine acids of the formula I

< / BR>
in which Y represents a C-organic radical,

through the reaction of Pinner interaction achilleid formula II

< / BR>
with alcohol and the subsequent interaction of the formed in the Pinner reaction of ester of the formula IV

< / BR>
a) with hydroxylamine to obtain the oxime of the formula V

< / BR>
methylation of the oxime of the formula V to oximoula ether formdata oximoula ester of formula VI with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III

R - OH,

boiling point which is above the 75oC.

2. The method of producing methylamino-methoxykynuramine acids of the formula I on p. 1 through reaction of Pinner interaction achilleid formula II

< / BR>
with alcohol and the subsequent interaction of the formed in the reaction of Pinner mixture of ester of the formula IV

< / BR>
and the amide of formula IV'

< / BR>
a) with hydroxylamine to obtain the oxime of the formula V

< / BR>
methylation of the oxime of the formula V to oximoula ether of the formula VI

< / BR>
or b) with O-methylhydroxylamine obtaining oximoula ether of the formula VI and the subsequent interaction oximoula ester of formula VI with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III

R - OH,

boiling point which is above the 75oC.

3. The method of producing methylamino-methoxykynuramine acids of formula I under item 1 or 2, characterized in that the conversion to the oxime of the formula V is carried out in the presence of the same alcohol of the formula III, which is used in the reaction of Pinner.

4. The method of producing methylamino --methoxykynuramine acids of formula I, p is as in the formula III, which is used in the reaction of Pinner.

5. The method according to PP. 1 to 4, characterized in that use alcohol of the formula III having a boiling point above 90oC.

6. The method of producing methylamino-methoxykynuramine acids of the formula IA

< / BR>
in which the substituents have the following meanings:

R1means hydrogen, hydroxy, mercapto, cyano, nitro, halogen, optionally substituted alkylsulfonyl, optionally substituted, alkylsulfonate, optionally substituted cycloalkyl, optionally substituted, aryloxy, optionally substituted arylsulfonyl, optionally substituted, arylsulfonyl, optionally substituted heterocyclyl or optionally substituted, getariako

or

Randmeans cyano, nitro, halogen, -C1- C4alkyl, C1- C4halogenated,1- C4alkoxy or1- C4halogenoalkane;

m denotes 0 or an integer in the range from 1 to 4, and the radicals Randcan be different, if m > 1;

Rbmeans hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, quinil, heterocyclyl, alkylaryl, cycloalkylcarbonyl, alkenylboronic, alkenylestersulfide or group C(R')=NOR";

R' means hydrogen, hydroxy, cyano, nitro, amino, halogen, optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino, alkenyl, alkenylacyl, alkanity, alkenylamine, quinil, alkyloxy, alkylthio, alkylamino, cycloalkyl, cycloalkene, cycloalkylation, cyclooctylamine, cycloalkenyl, cycloalkenyl, cycloalkenyl, cyclooctylamine, heterocyclyl, heterocyclic, heterocyclic, heterocyclisation, aryl, aryloxy, aaltio, arylamino, heteroaryl, heteroaromatic, heteroaromatic or heteroarenes;

R means hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, quinil, heterocyclyl, aryl or heteroaryl;

Rcrepresents a group specified for Rbor hydroxy, cyano, nitro, amino, halogen, optionally substituted alkoxy, alkylthio, alkylamino, dialkylamino, aryloxy, aaltio, arylamino, getariako, getarity or hetarylamino,

or Rband Rwithboth together with the atom to which they are linked, represent a carbocyclic or heterocyclic ring,

through the reaction of Pinner interaction achilleid formula IIA

< / BR>
with alcohol and the subsequent interaction of the image is ormula VA

< / BR>
methylation of the oxime of formula VA to oximoula ether of the formula VIA

< / BR>
or b) with O-methylhydroxylamine obtaining oximoula ether of the formula VIA and the subsequent interaction oximoula ether of the formula VIA c-methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III

R - OH,

boiling point which is above the 75oC.

7. The method of producing methylamino-methoxykynuramine acids of the formula IA according to p. 6, through the reaction of Pinner interaction achilleid formula IIA

< / BR>
with alcohol and the subsequent interaction of the formed in the reaction of Pinner mixture of ester of formula IVA

< / BR>
and amide of formula IV'A

< / BR>
a) with hydroxylamine to obtain the oxime of formula VA

< / BR>
methylation of the oxime of formula VA to oximoula ether of the formula VIA

< / BR>
or b) with O-methylhydroxylamine obtaining oximoula ether of the formula VIA and the subsequent interaction oximoula ether of the formula VIA with methylamine, characterized in that in the reaction of Pinner used alcohol of the formula III

R - OH,

boiling point which is above the 75oC.

8. The method of producing methylamino-methoxykynuramine acids of the formula IA po, which is used in the reaction of Pinner.

9. The method of producing methylamino --methoxykynuramine acids of formula IA under item 6 or 7, characterized in that the conversion in Joksimovic ether of formula VIA is carried out in the presence of the same alcohol of the formula III, which is used in the reaction of Pinner.

10. The method according to PP.6 to 9, characterized in that use alcohol of the formula III having a boiling point above 90oC.

11. Esters of General formula X

< / BR>
R represents the residue of an alcohol (R - OH), boiling point which is above the 75oC.

R1hydroxy, mercapto, cyano, nitro, halogen, optionally substituted alkylsulfonyl, optionally substituted cycloalkyl, optionally substituted, aryloxy, optionally substituted heterocyclyl or optionally substituted, getariako,

< / BR>
or

< / BR>
and Ra, Rband Rwithhave the values listed in paragraph 6,

Z denotes O, NOH or NOCH3with the exception of compounds in which Z is oxygen or NOCH3, R1represents a group

< / BR>
in which Rbmeans methyl and Rwith- optionally substituted phenyl.

 

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The invention relates to new chemical compounds having valuable properties, in particular to new derivatives of sulfonamidophenylhydrazine

The invention relates to the production of 1-arestriction formula I, where R is lower alkyl; X is halogen, lower alkyl, nitro, hydroxy, -NHSO2R', -Ni(SO2R')2, -N(R')SO2R'; R' is lower alkyl; n is an integer from 0 to 3, processing of arestriction formula II halogenoacetyl acid or its salt in the environment tert-butanol - water at a weight ratio of (95-70):(5-30), respectively

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Pesticides // 2142938
The invention relates to a new one with pesticidal activity of the compounds of the formula I

< / BR>
and its isomers and mixtures of isomers, if any, where either

a) X represents a nitrogen atom and

Y means OR11or N(R12R13or

b) X is CH and

Y means OR11< / BR>
and where next

R11means C1-4alkyl;

R12and R13independently mean hydrogen or C1-C4alkyl;

A denotes an O atom or the group NR4;

R1means hydrogen, C1-C4alkyl, halogen-(C1-C4alkyl, cyclopropyl, cyano or methylthio,

R2means hydrogen, C1-C6alkyl, C3-C6cycloalkyl, group

< / BR>
group

< / BR>
or thienyl;

D represents the same or different radicals and represent halogen, C1-C4alkyl, C1-C4alkoxy, C1-C2haloalkyl, C1-C2haloalkoxy,

C3-C6alkenylacyl, C3-C6alkyloxy, C1-C4alkylenedioxy)-O-, -S(O)m-, -(C1-C4alkyl)-S(O)m-, -S(O)m-(C1-C4alkyl)-,

m is 0, 1 or 2,

B means C1-C6alkyl, halogen-(C1-C6alkyl, C3-C6cycloalkyl or means C2-C6alkenyl or C2-C4quinil-C1-C2alkyl, each of which is unsubstituted or substituted by 1-3 halogen atoms, or denotes aryl or heterocyclyl, each of these two substituents independently unsubstituted or mono-pentosanase C1-C6by alkyl, halogen-(C1-C6by alkyl, halogen, C1-C6alkoxygroup or halogen-C1-C6alkoxygroup, or group

< / BR>
or trimethylsilyl;

and

R5, R6, R7, R8and R9independently mean hydrogen, C1-C4alkyl or halogen, and

p is 0, 1, 2 or 3;

R3means hydrogen, C1-C6alkyl, C1-C6haloalkyl containing 1 to 5 halogen atoms, C1-C4alkoxy-C1-C2alkyl, C2-C4alkenyl-C1-C2alkyl, which is unsubstituted or substituted by 1-3 halogen atoms, C2-C4quinil-C1-C2alkyl, C3-Calkyl, which is unsubstituted or is substituted by 1-4 halogen atoms, cyan-C1-C4alkyl, C1-C4alkoxycarbonyl-C1-C2alkyl, C1-C4alkoxycarbonyl-C1-C2alkyl, phenyl-C1-C3salkil, which is unsubstituted or substituted with halogen, C1-C3the alkyl, C1-C4alkoxygroup, C1-C4haloalkyl, a cyano, a nitro-group or C1-C4alkylenedioxy, and the phenyl group may be mono-, di - and tizanidine identical or different substituents; phenyl, which is unsubstituted or mono - or Disaese independently C1-C4the alkyl, C1-C4alkoxygroup, halogen, C1-C2haloalkyl containing 1-3 halogen atom, a nitro-group, or by cyano, or pyridyl, which is unsubstituted or mono - or Disaese independently C1-C4the alkyl, C1-C4alkoxygroup, halogen, C1-C2haloalkyl containing 1-3 halogen atom, a nitro-group, or cyano;

R4means C1-C4alkyl, phenyl or

R3and R4together with the nitrogen atom to which they are attached, form a saturated or unsaturated 5-7-membered ring that Nezami of N, O and S;

with the exception of compounds of the formula I, where, if

X represents CH,

Y means OCH3,

A denotes an oxygen atom,

R1means hydrogen and

R3means methyl;

R2is not phenyl and substituted only by one or more chlorine atoms

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The invention relates to a new above-mentioned compounds, method of their production and the means of containing this compound, useful for combating fungi and insect pests

The invention relates to new substituted simple aximum esters of General formula I

< / BR>
in which

R1represents C1-C6-alkyl, C3-C6alkenyl, C3-C4-quinil, C1-C6-halogenated, C3-C6-halogenoalkanes, C1-C4-alkoxy-C1-C6-alkyl,

C1-C6-alkoxycarbonyl-C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C6-alkyl, phenyl-C1-C6-alkyl, phenyloxy-C1-C6-alkyl, and phenyl may be substituted with halogen; cyan-C1-C6-alkyl, phenyl-C3-C6alkenyl, and phenyl may be substituted with halogen, C1-C2-halogenation; furan-2-yl-C1-C6-alkyl;

R2and R3are identical or different and denote hydrogen, C1-C4-alkyl, C1-C4-alkoxygroup, halogen, cyano or nitro-group;

R4denotes hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, halogen-C1-C7-alkyl, phenyl;

R5and R6are identical or different and denote hydrogen or C1-C<

The invention relates to the synthesis of compounds of the class of substituted salicylaldoxime that can be used as complexing agents for non-ferrous, rare and heavy metals in the composition of the extractant
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