Dearlove esters, methods for their preparation containing herbicide composition, intermediate compounds, method for their preparation and method of weed control and desiccation of plants

 

(57) Abstract:

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. Also disclosed are several methods of obtaining these compounds, intermediate compounds and herbicide composition on the basis of these new girilovich esters. In addition, the proposed method of weed control and desiccation of plants comprising applying to the locus of these compounds. 12 C. and 9 C.p. f-crystals, 26 PL.

Class girilovich esters, which, as well as compositions based on them, are used in weed control, has a General formula

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where X, Y represent hydrogen, halogen, cyano, nitro or C1-6-halogenated;

Z represents oxygen or sulfur;

Q is selected among

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Ar is C is excluded substituted phenyl.

There are various substituted phenyl esters (I')

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Q can represent pyrazole, imidazole, imidazolidine-2,4-dione, triazoline, tetryzoline, aminouracil, etc. R may represent hydrogen, alkyl, cycloalkyl, alkenyl or quinil. In U.S. patent 5496956 describes arylpyrazole with a group R, is selected among propargyl, allyl or substituted alkyl. In the Japan patent JP 6256312 describes phenylimidazole with a group R, is selected among hydrogen, C1-10-alkyl, C1-5-halogenoalkane, C3-5-alkenyl, C3-5-quinil or C3-6-cycloalkyl. In U.S. patent 5125958 describes triazolinone with the substituted phenyl group is selected as the group R. In the Japan patent JP 57197268 describes the hydantoins with the lower alkyl group is selected as the group R. In U.S. patent 4902337 written off the hydantoins with a group R, is selected among hydrogen, alkyl, cycloalkyl, alkenyl or quinil. In the Japan patent JP 525173 describes pyrimidinedione with a group R, is selected among hydrogen, C1-10-alkyl, C1-5-halogenoalkane, C3-5-alkenyl, C3-5-quinil or C3-6-cycloalkyl. In U.S. patent 4985065 describes phenyltetrazole selected as group R is a substituted phenyl group. About what uppoi R, selected from among hydrogen, alkyl, cycloalkyl, alkenyl or quinil. In U.S. patent 4452981 describes phenylurazole with a group R, is selected among C1-3-alkyl, allyl or propargyl. In EP-A-517181 (corresponding to U.S. patent 5280010) describes aminouracil compounds in which Q represents aminouracil, and R represents a lower alkyl group. In WO 96/07323 and WO 96/08151 describes some of the known compounds of uracil. In WO 96/08151 General idea is much broader than what is disclosed in the claims and in earlier patents. Specific aminouracil formula (I) below, are unknown and are new.

The present invention shows that some dearlove esters represented by the General formula (I) or their salts have a strong herbicide action with sufficient security for cultivated plants.

There remains a need for new and more effective herbicide compounds and compositions. This invention relates to new derilova esters, compositions containing dearlove esters and to the use girilovich esters and compositions on their basis as broad spectrum herbicides that are effective against monocotyledonous is topasna for cultivated plants. Compounds and compositions of the present invention can sometimes be used as desicant. The invention also includes methods of obtaining these compounds and intermediates for these compounds, and methods of using compounds as herbicides.

This invention relates to derilova esters of General formula I and their salts

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where X, Y represent, independently, hydrogen, halogen, cyano, nitro or C1-6-halogenated, and

Z represents oxygen or sulfur, and

Q choose among

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R1represents halogen;

R2, R3, R4and R5represent, independently, hydrogen, C1-6-alkyl or C1-6-halogenated;

when R3and R4taken together with the atoms to which they are attached, form a four-semiline substituted or unsubstituted ring, optionally interrupted with O, S(O)nor N-R4and optionally substituted with one to three C1-6-alkyl groups or by one or more halogen atoms;

R6represents hydrogen, C1-6-alkyl, C2-6alkenyl, C2-6-quinil, C1-6-halogenated, C2-6-halogenoalkanes, C2-6-halogenoalkanes, C2represent, independently, oxygen, or sulfur;

In represents CH or N;

each of R7and R8is, independently, hydrogen, C1-6-alkyl, optionally substituted by one or more halogen atoms, or C3-6-cycloalkyl, optionally substituted by one or more halogen atoms, and when R7and R8taken together with the atoms to which they are attached, they represent a four-semiline substituted or unsubstituted ring, optionally interrupted with O, S(O)nor N-R4and optionally substituted with one to three C1-6-alkyl groups or by one or more halogen atoms;

n represents the integer 0, 1 or 2;

R9and R10represents hydrogen, C1-6-alkyl, acyl or C1-6-alkylsulfonyl, or R9and R10may form a ring consisting of polymethene group (CH2)mwhere m is an integer of 2, 3, 4 or 5, together with the nitrogen atom of the group NR9R10that may or may not have C1-6-alkyl substituent.

Some compounds of formula (I) and their intermediate compounds can sometimes exist in the form of geometric or optical isomers, megatokyo compounds can form salts with acidic substances of the nature or substance of the main character. Salt with the acidic substance may be a salt of an inorganic acid such as hydrochloride, hydrobromide, phosphate, sulfate or nitrate. Salt with the substance of the main character can represent a salt of an inorganic or organic base, such as sodium salt, potassium salt, calcium salt, salt of Quaternary ammonium bases, such as ammonium salt or dimethylamine salt.

AG represents a substituted or unsubstituted aryl or heteroaryl ring; when Q is Q3or Q6excluded substituted phenyl.

This invention also relates to compositions containing these compounds, and to methods of using these compounds and compositions. Compounds and compositions of the present invention is particularly useful for the selective combating undesirable plant species, sometimes in the presence of cultivated plants. Compounds and compositions of the present invention can also be used as desicant.

The present invention relates to a method of controlling undesirable plant species by pre-emergence or post-harvest applications.

Dearlove esters of this invention have a General formula I1-6-alkyl, halogen-(C1-6-alkyl, C1-6-alkoxy, halogen-(C1-6-alkoxy, C1-6-alkylthio, C1-6-alkylsulfonyl, C1-6-alkylsulfonyl, C1-6-dialkylaminoalkyl, cyano, nitro, amino, hydroxy, C1-6-alkylsulfonyl, C1-6-alkoxycarbonyl-C1-6-alkoxy, C1-6-alkylcarboxylic, bisbenzimide, aminoacetyl, aminotetralin or amino-C1-6-arylsulfonate. The number of substituents is one or more, e.g. up to five. When this number is two or more, the substituents may be the same or different.

The alkyl group and the alkyl portion of the definition relating to X, Y, R2-R10and the substituents in the case of substituted aryl and heteroaryl rings as AG contain linear or branched chain C1-6preferably C1-4still6also contain linear or branched chain, chain C2-6preferably C2-4such as vinyl, propenyl, butenyl, pentenyl, hexenyl, ethinyl, PROPYNYL, butynyl, pentenyl or hexenyl.

Halogen atom and halogenates in the definition related to X, Y, R1-R8represent the atoms fluorine, chlorine, bromine or iodine. Halogenation, halogenation or galogenangidridy the group consisting of alkyl, alkenylphenol or alkenylphenol group and one or more halogen atoms mentioned above. When the number of halogen atoms is equal to two or more halogen atoms may be the same or different.

Preferred compounds of formula I of this invention are compounds

where X, Y represent, independently, hydrogen or halogen;

Z represents oxygen or sulfur;

Q is selected among Q1, Q2, Q4, Q6, Q7, Q8or Q9.

Ar is pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazole or phenyl, or pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazole or phenyl substituted by substituents up to five selected, independently, among the atoms of bromine, chlorine, fluorine, iodine, (C1-C4)-alkylsulfonyl, C1-4-alkylsulfonyl, di-C1-4-alkylaminocarbonyl, cyano, nitro, amino, hydroxy, C1-4-alkylsulfonyl, C1-4-alkoxycarbonyl-C1-4-alkoxy or C1-4-alkoxycarbonyl; when Q is Q6substituted phenyl is excluded.

The most preferred compounds of this invention are the compounds of formula I,

where X is fluorine;

Y represents chlorine;

Z represents oxygen or sulfur;

Q is selected among Q1, Q2, Q4ABOUT6ABOUT7, Q8or Q9;

Ar represents 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 5-amino-2-pyridyl, 3-dimethylaminoethyl-2-pyridyl, 3-methylsulphonyl-2-pyridyl, 3-isopropylphenyl-2-pyridyl, 6-chloro-3-trifluoromethyl-2-pyridyl, 3,5,6-cryptosporidial, 2 pirimidil, 4 pirimidil, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dime atrovenr, 4-nitrophenyl, 4-AMINOPHENYL, 4-hydroxyphenyl, 4-methylsulfonylamino, 4-(1-ethoxycarbonylmethoxy)phenyl, 2-cyanophenyl, 2-cyano-3-forfinal, 2-cyano-4-forfinal, 2-amino-4-(1-ethoxycarbonylmethoxy)phenyl, 2-cyano-4-nitrophenyl, 4-amino-2-cyanophenyl, 4-nitro-2-triptoreline, 4-amino-2-triptoreline, 4-acetylamino-2-triptoreline, 4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolin or 5-nitro-2-thiazolyl; when Q is Q6substituted phenyl is excluded.

Intermediate compounds II and III can be obtained by the methods specified in the method (1).

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Method 1

Method (1) is carried out in two stages. The first stage is the interaction of aminophenol with arylhalides or heteroarylboronic with or without solvents. The solvent may be acetonitrile, tetrahydrofuran, dimethylimidazolidin, dimethylsulfoxide, hexamethylphosphoramide, N,N-dimethylformamide, acetone, butane-2-it, benzene, toluene or xylene, in the presence of a base such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, tert-piperonyl potassium fluoride, potassium or sodium hydride. The catalysts can be used, but you can not use lady (0), the tetrabutylammonium halides or 8-hinolinol. The reaction temperature is usually from 0 to 250oC, preferably from 20 to 120oC. the reaction Time is from 1 to 12 hours, preferably from 2 to 6 hours. Diarylethene (II) can also be obtained by processing the aminophenol arylesterase tricarboxylate, triphenylbismuth diacetate, trifurcation triphenylbismuth or diphenyliodonium in the presence of solvents such as benzene, toluene, dichloromethane, dichloroethane, chloroform or water, with or without catalysts, such as copper or a transition metal. The temperature generally ranges from 0oC to the boiling point of the mixture, and the reaction time is from 10 minutes to 72 hours. The preferred temperature of 20oC to the boiling point of the mixture, and the time is preferably from 2 to 6 hours.

The second stage requires the processing of amine (II) with phosgene or triphosgene in a solvent such as hexane, heptane, benzene, toluene, xylene or ethyl acetate. The reaction temperature is usually from 0oC to the boiling point of the mixture, preferably the boiling point of the mixture. The reaction time is usually from 30 minutes to 6 hours, preferably from 2 to 3 hour stage method (1).

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Method 3

When the method (3) simple ester bond is formed using the conditions described in the first stage of the method (1).

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Method 4

Method (4) is carried out in three stages. In the first stage is the formation of a diazonium salt of aniline (II), usually in an acidic environment, such as concentrated hydrochloric acid, while processing an aqueous solution of sodium nitrite. He is recovering in the presence of a reducing agent with formation of the corresponding derivative of hydrazine. This reducing agent may be an inorganic compound such as hydrated tin chloride(II). The mixture is processed by ketokislot, such as pyruvic acid, in aqueous solution. The reaction temperature is from -15 to 30oC, and the reaction time is from 30 minutes to 4 hours. The preferred first temperature is from 0 to 5oWith, and later 20-30oWith, and the preferred time is from 30 to 60 minutes.

In the second stage the obtained hydrazone (VIII) is treated with diphenylphosphorylacetate in an inert solvent, such as benzene, toluene, xylene, hexane, in the presence of a base such as triethylamine or pyridine. The reaction temperature leaves from the 20oVlaamse boiling point of the mixture, and the time is from 1 to 2 hours.

The final stage is the alkylation of (IX) in an inert solvent, such as diethyl ether, dioxane or tetrahydrofuran, an alkylating agent, such as alkylhalogenide, halogenoalkane or alkylsulfate, in the presence of a base such as sodium hydroxide or potassium hydroxide, sodium carbonate or potassium hydroxide, pyridine or triethylamine, with or without catalytic amounts tetraalkylammonium salt. The reaction temperature ranges from -40 to 50oC, and the reaction time is from 30 minutes to 4 days. The preferred reaction temperature is from 20 to 30oWith, the preferred reaction time of 2 days.

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Method 5

Method (5) is carried out in three stages. The first stage is the preparation of isocyanate (IIIa) with ammonia in an inert solvent, such as hexane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran or dioxane. The reaction temperature is from -10 to 100oC, and the reaction time ranges from 15 minutes to 6 hours. Preferably the reaction temperature is from 0 to 10oC, and the reaction time is from 30 to 60 minutes.

The second step is the processing of urea (IX) an acid catalyst such as p-colorcontrol, hexane, at a temperature of 20oC to the boiling point of the mixture, from 10 to 24 hours, with the formation of imidazolidinone (XII). The temperature is preferably the boiling point of the mixture, and the time is 12-16 hours.

The final stage is the alkylation of (XII) in an inert solvent, such as diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, xylene or hexane, an alkylating agent, such as alkylhalogenide or halogenoalkane, in the presence of a base such as sodium hydroxide or potassium hydroxide, sodium carbonate or potassium hydroxide, pyridine or triethylamine. The reaction temperature is from 20oC to the boiling point of the mixture, and the time is from 30 minutes to 20 hours. Preferably the temperature is from 50 to 100oWith, and the time - from 12 to 16 hours.

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Method 6

Method (6) is carried out in three stages. The first stage is the processing of the isocyanate (III-b) 2,2-dimethyl-5-(2-tetrahydropyrimidin)-1,3-dioxane-4,6-dione in the presence of a base such as sodium methoxide, ethoxide sodium tert-piperonyl potassium or sodium hydride, in a solvent such as toluene, N,N-dimethylformamide or dimethylsulfoxide. The reaction temperature ranges from -40oWith deagle connection is from -30 to -20oAnd then for the reaction requires temperatures of 100 to 120oC. the Preferred time is between 4 to 5 hours.

The second stage is the hydrolysis of simple essential link in the acidic conditions in an inert solvent, such as chloroform or methylene chloride, with the use of concentrated sulfuric acid. The reaction temperature is from -20 to 50oWith, and the time is from 30 minutes to 6 hours. Preferably, the joining is carried out at 0-5oAnd then for the reaction requires temperatures from 20 to 30oC. the Preferred time is from 1 to 2 hours.

At the final stage when using the conditions described in the first stage of the method (1), it forms a simple radio link.

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Method 7

Method (7) is carried out in two stages. In the first stage is the formation of tetrazole ring (XVIII) during the processing of the isocyanate (III) trimethylsilylmethyl with or without solvent. The reaction temperature is from 100oC to the boiling point of the mixture, and the time is from 1 to 48 hours. Preferably the reaction temperature is the boiling point of the mixture, and the time is 24 hours.

The final stage is Alcolor, xylene, hexane, N,N-dimethylformamide or dimethylsulfoxide, alkylating agent, such as alkylhalogenide or halogenoalkane, in the presence of a base such as sodium hydroxide or potassium hydroxide, sodium carbonate or potassium hydroxide, pyridine or triethylamine. The reaction temperature ranges from 50 to 150oC, and the reaction time is from 30 minutes to 2 days. The preferred temperature range is from 70 to 90oWith, and the time from 20 to 30 hours.

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Method 8

Method (8) is carried out in five stages. In the first stage are processed amine (II) thiophosgene in a solvent such as hexane, heptane, benzene, toluene, xylene or ethyl acetate. The reaction temperature is usually from 0oC to the boiling point of the mixture, preferably the joining is carried out at a temperature of from 0 to 5oAnd then for the reaction requires a temperature for heating the mixture to a boil. The reaction time is usually from 30 minutes to 6 hours, preferably from 2 to 3 hours.

In the second stage isothiocyanate (XX) is treated with formic hydrazide in an inert solvent, such as toluene, tetrahydrofuran, dioxane or diethyl ether. The reaction temperature is usually from 0OI is usually from 30 minutes to 10 hours, preferably from 3 to 4 hours.

Formylhydrazine (XXI) is treated with phosgene or triphosgene in a solvent such as hexane, heptane, benzene, toluene, xylene, acetone, or ethyl acetate. The reaction temperature is usually from -20 to 50oC, preferably from 0 to 25oC. the reaction Time is usually from 30 minutes to 6 hours, preferably from 1 to 2 hours.

Hydrolysis of 3-formilthiazoline (XXII) is carried out under acidic conditions in solvents such as acetone, butane-2-he, methanol, ethanol, tetrahydrofuran or N,N-dimethylformamide. Acid can imagine sulfuric, hydrochloric or acetic acid and can be diluted. The reaction temperature is usually from -20oWith up to 50, preferably from 0 to 25oC. the reaction Time is usually from 15 minutes to 6 hours, preferably from 30 minutes to 2 hours.

The final stage is the alkylation of (XXIII) in an inert solvent, such as acetone, diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, xylene, hexane, N,N-dimethylformamide or dimethylsulfoxide, alkylating agent, such as alkylhalogenide or halogenoalkane, in the presence of a base such as sodium hydroxide or potassium, the options boil the mixture, and the time is from 30 minutes to 6 hours. The preferred temperature range is from 50 to 90oWith, and the time - from 1 to 3 hours.

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Method 9

According to the method of (9) amines (II) is converted into 2,4-imidazolidinedione (XXVII) in three stages. In the first stage processing galogenangidridy halogenases acid, such as chloracetamide, and an organic base such as triethylamine or pyridine, in an inert solvent, such as benzene, toluene, xylene, tetragidrofuran or N, N-dimethylformamide, gives chloramide (XXV). Preferred allermuir agent is chlorocatechol, and the preferred base is triethylamine. The preferred solvent is toluene. The reaction may be carried out at temperatures from -20 to 150oC, preferably from 25 to 50oC. the reaction Time can range from 30 minutes to ten hours, preferably from 2 to 4 hours.

In the second stage, the interaction of these chloramide (XXV) with the appropriate amines in a solvent such as alcohols C1-5, tetrahydrofuran or dioxane, gives aminoamide (XXVI). The preferred solvent is ethanol, and the reaction can be carried out at temperatures from -20 to 150oC, preferably from 25 to 7

At the third stage aminoamide (XXVI) are processed 1,1'-carbonyl diimidazol in an inert solvent, such as benzene, toluene, xylene, tetrahydrofuran or N,N-dimethylformamide, and formed 2,4-imidazolidinedione (XXVII). The preferred solvent is toluene, and the reaction can be carried out at temperatures from -20 to 150oC, preferably from 100 to 120oC. the reaction Time can range from 30 minutes to ten hours, preferably from 2 to 3 hours.

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Method 10

The method (10) is carried out in three stages. The first stage is the interaction of the isocyanate (HHA) with saturated heterocyclic compound (XXVIII), such as 1-ethoxycarbonylpyrimidine, where In=N, and f=2, which is optional, can be implemented in two stages - (1) and (2). At stage (1) the reactants are mixed together in an inert solvent, such as benzene, toluene, xylene, dioxane, hexane, ethyl acetate, tetrahydrofuran, diethyl ether or acetone. The reaction temperature is usually from -70oC to the boiling point of the mixture, depending on the nature of V, f and R4. The reaction time is usually from 30 minutes to 20 hours, depending on the nature of V, f and R4. At step (2) after removal of the solvent mo occurs at a temperature of from 50oC to the boiling point of the mixture, and the time is from 6 hours to 3 days. The preferred temperature is the boiling point of the mixture, and the time is from 20 to 30 hours.

The second step is the hydrolysis of simple essential link in the acidic conditions in an inert solvent, such as chloroform or methylene chloride, using concentrated sulfuric acid. The reaction temperature is from -20 to 50oWith, and the time is from 30 minutes to 6 hours. The preferred temperature at 0oWith time and from 1 to 2 hours.

The final stage is the formation of simple essential communication and receiving (XXXI). This is done under the conditions described in the first stage of the method (1).

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Method 11

Method (11) is the one-stage method, where the connection (b), which may represent isocyanate or isothiocyanate interacts with saturated heterocyclic compound (XXVIII), with or without solvent, with the formation of reaction product (XXXI). The interaction is enhanced in the presence of solvents such as hexane, pentane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, acetone, butane-2, ethyl acetate, N, N-dimethylformamide or dimethylsulfoxide is preferably from 0 to 30oWith, and the time - from 15 minutes to 12 hours.

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Way 12

According to the method of (12) thiadiazolidine (XXIV) are treated with a catalytic amount of base such as sodium methoxide, ethoxide or sodium tert-piperonyl potassium in alcohol C1-5such as methanol, ethanol or tert-butanol, at a temperature of from 0oC to the boiling point of the mixture for a time of from 15 minutes to 3 hours. The preferred boiling point of the mixture and the time from 30 to 60 minutes.

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Way 13

Method (13) is carried out using 0.5 to 10 equivalents, preferably 0.8 to 3) of hydrazine with respect to oxazepam (XXXII). Examples of hydrazines include hydrazine, acylhydrazone, such as methyl-, ethyl - or tert-butylhydrazine, and cyclic hydrazines, such as 1-aminopyrrolidine. The reaction proceeds without any solvent, but is usually accelerated by using a solvent.

Also required for the reaction solvents, such as aliphatic hydrocarbons, for example hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers, such as diethyl eviternity, tertiary amines, such as pyridine and N,N-dimethylaniline, acid amides, such as N,N-dimethylacetamide, N,N-dimethylformamide and N is an organic, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, alcohols, such as methanol, ethanol, propanol and butanol, water and mixtures thereof.

The reaction temperature is usually from -30 to 150oC, preferably from -10oC to the boiling temperature of the reaction mixture. For the reaction typically takes from 10 minutes to 96 hours, preferably from 30 minutes to 48 hours.

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Way 14

According to the method of (14) ether bond is formed when using the conditions described in the first stage of the method (1).

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Way 15

Method (15) is carried out in a solvent such as dioxane, dimethylsulfoxide, hexamethylphosphoramide or N,N-dimethylformamide, in the presence of a base such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or sodium hydride. You can use a number of agents amination, such as 2,4-dinitrophenoxy; O-arylsulfonamides, such as 2,3,6-trimethyl - and triisopropylphenylsulfonyl; O-philguarantee and O-methicillinresistant. The reaction temperature is usually from -30 to 110oC. the reaction Time is preferably from 12 hours to 3 days.

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Way 16

Using the method of (16) can be used isocyanate (III) for the formation of aminouracil (Hhhe) by synthesis in the same reactor without isolation of uracil (XXXV). Uracile ring is formed by the interaction of the resulting isocyanate (III) with alkyl-3-amino-4,4,4-trifurcation and a base such as sodium hydride, sodium methoxide or ethoxide sodium in a solvent such as dimethylsulfoxide, N,N-dimethylformamide, benzene, toluene, xylene, tetrahydrofuran, dioxane or diethyl ether, at temperatures usually from -50 to 50oWith, when the reaction time from 10 minutes to 14 hours. The preferred reaction temperature is from -30 to 30oC and the reaction time is from 15 minutes to 6 hours. Then entered the amination agents, such as 2,4-dinitrophenoxy; O-arylsulfonamides, such as 2,3,6-trimethyl - and triisopropylphenylsulfonyl; O-philguarantee and O-methicillinresistant, as described in method (15). The reaction temperature is usually from -30 to 110oC, and the reaction time is from 12 hours to 7 days. The reaction temperature preferably ranges from 20 to 30oC. the reaction Time is preferably about), where A1and/or A2represent a sulfur atom, can be obtained by reaction of compounds of the above formula (XXXIII) with a sulfurization agent, such as reagent Losson or pentasulfide phosphorus. Next, sulfurization may occur on prolonged heating with excess reagent. For the reaction solvents are used, such as benzene, toluene and xylene. The reaction time is usually from 2 to 12 hours, preferably 3-4 hours. The reaction temperature is usually from 0 to 150oC, preferably from 60oC to the boiling point of the mixture.

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Method 18

According to the method of (18) ether bond is formed under the conditions described in the first stage of the method (1).

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Method 19

According to the method of (19) requires the interaction of sodium or potassium salt of an aromatic or heterocyclic hydroxyl-containing compounds with halogenations uracil (XXXVIII). The reaction proceeds in the absence of any solvent, but is usually accelerated by using a solvent. Such solvents include toluene, xylene, N,N-dimethylformamide and dimethylsulfoxide, and used catalyst, such as copper, bronze or a transition metal. Temperature Oba is no 150oC to the boiling point of the mixture, and the time is preferably from 2 to 6 hours.

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Method 20

The method (20) shows that uracile ring can be formed by the interaction of the resulting isocyanate (III) with alkyl-3-amino-4,4,4-trifurcation and a base such as sodium hydride, sodium methoxide, ethoxide or sodium tert-piperonyl potassium in a solvent such as dimethylsulfoxide, N, N-dimethylformamide, benzene, toluene, xylene, tetrahydrofuran, dioxane or diethyl ether, usually at temperatures from -50 to 50oWith, when the reaction time from 10 minutes to 14 hours. The preferred temperature is from -30 to 30oWhen the reaction time from 15 minutes to 6 hours.

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Method 21

Method (21) is carried out in two stages. The first stage is to obtain N-phenylacetamide (XXXIX) using conventional methodology.

The second step is the cyclization with the formation of oxazino (XXXII). This stage is carried out in solvents, representing aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, tertiary amines such as pyridine and N,N-dimethylaniline, amides, acids, t is ethylsulfonyl and sulfolan, and organic acids such as formic acid, acetic acid, lactic acid, and acetic anhydride. Preferably used are the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons and organic acids. The reaction temperature is usually from 0 to 200oC, preferably from 20oC to the boiling point of the mixture. The reaction time is from 10 minutes to 72 hours, preferably from 30 minutes to 24 hours.

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Method 22

Method (22) is carried out in two stages. The first stage is the formation of phenoloxidase (XL) using the techniques described in method (21). The process is carried out in solvents, representing aliphatic hydrocarbons such as hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, tertiary amines such as pyridine and N,N-dimethylaniline, acid amides, such as N,N-dimethylacetamide, N,N-dimethylformamide and N is an organic, sulfur-containing compounds such as dimethylsulfoxide and sulfolane, and organic acids such as formic acid, acetic acid, lactic acid, and acetic anhydride. Preferably used above Eliphalet from 0 to 200oC, preferably from 20oC to the boiling point of the mixture. The reaction time is from 10 minutes to 72 hours, preferably from 30 minutes to 24 hours.

The second stage is carried out under the same conditions as described for the method (13).

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Method 23

Method (23) is carried out in two stages. Source materials for the first stage carbamates (XLI) are obtained by conventional methodology. They are processed alkyl-3-amino-4,4,4-trifurcation under the conditions described for the method (20). The second stage is carried out under the same conditions as described for the method (15).

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Method 24

When the method (24) isocyanate (III) is handled by hydrazinonicotinamide (XLIII) under the same conditions as described for the method (20), with the formation of the desired reaction product (XXXIII).

Although the following describes some of the variants of embodiment of the present invention, the scope of the present invention is not limited to these options.

Will be described examples of preparing compounds of the present invention. Obtaining 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione is described in U.S. patent 4859229. The reagent Losson [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphate-2,4-d is achet "concentrated", and so pl." refers to melting point. Processing, process" indicates that the added water and ethyl acetate solutions are separated, and the organic phase is dried over sodium sulfate, filtered, and the filtrate pariveda under reduced pressure. Obtaining 5-amino-2-chloro-4-terfenol described in U.S. patent 4484941. Purity is assessed by thin-layer chromatography, liquid chromatography, and monitored using spectra1H and13Nuclear magnetic resonance (NMR), which is obtained on the Varian instrument, 300 MHz.

Example 1

Synthesis of 4-chloro-2-fluoro-5-(2-pyrimidinone)phenylisocyanate (intermediate connection S)

(Method 1)

1.1.

2-(5-Amino-2-chloro-4-pertenece)pyrimidine (intermediate compound IIp)

A mixture of 5-amino-2-chloro-4-terfenol (3.57 g), potassium carbonate (3.04 from g) and 2-chloropyrimidine (3,20 g) is suspended in butane-2-one (100 ml) and dimethyl sulfoxide (10 ml), and refluxed overnight. The solution process and subjected to chromatography on silica gel with elution with a mixture of ethyl acetate and hexane, 1:2, and receives a yellow crystals (4.0 g).

1H NMR (acetone-d6, TMS): 4,75 (2H, Ushs), is 6.78 (1H, d, J=8,4 Hz), to 7.09 (1H, d, J=a 10.6 Hz), to 7.15 (1H, t

2-(5-amino-2-chloro-4-pertenece)-4-chloropyrimidine (intermediate connection IIq).

2-(5-amino-2-chloro-4-pertenece)-4,6-dimethoxypyrimidine (intermediate compound IIr).

2-(5-amino-2,4-dichlorphenoxy)-4-chloropyrimidine (intermediate compound IIs).

2-(5-amino-2-cotton-4-pertenece)-nitrobenzene (intermediate compound IIt).

2-(5-amino-2-chloro-4-pertenece)-benzonitrile (intermediate compound IIu).

2-(5-amino-2-chloro-4-pertenece)-6-perbenzoate (intermediate compound I-IV).

1.2

4-chloro-2-fluoro-5-(2-pyrimidinone)phenylisocyanate (intermediate connection S)

The solution triphosgene (1,21 g) in ethyl acetate (10 ml) stirred at 0oIn nitrogen atmosphere, and at this time is added dropwise a solution of 2-(5-amino-2-chloro-4-pertenece)pyrimidine (0.96 g) and triethylamine (1.2 ml) in ethyl acetate (10 ml). The mixture is refluxed for 3.5 hours, cooled, filtered, and the filtrate is evaporated, and receive the corresponding isocyanate.

1H NMR (Dl3, TMS): 7,03 (1H, d, J=7,2 Hz), 7,10 (1H, t, J=4,8 Hz), 7,31 (1H, d, J=8,9 Hz), to 8.57 (2H, d, J=4,8 Hz).

In this way it is possible to obtain the following compounds.

4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyrimid the intermediate connection E).

4-chloro-2-fluoro-5-(2-cianfrocca)phenylisocyanate (intermediate compound IIIf).

4-chloro-2-fluoro-5-(6-fluoro-2-cianfrocca)phenylisocyanate (intermediate compound IIIg).

Example 2

Synthesis of 4-chloro-3-(4-chloro-2-fluoro-5-(4,6-dimethoxy-2-triazinone)phenyl)-1-methyl-5-trifluoromethyl-lH-pyrazole (compound 1-8) (method 2)

4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-tricorner-1H-pyrazole (obtained by the method described in U.S. patent 5281571) (0.25 g, from 0.76 mmol) is dissolved in N,N-dimethylformamide (5 ml) and add potassium carbonate (0,13 g of 0.91 mmol) and 2-chloro-4,6-dimethoxytrityl (0.16 g, of 0.91 mmol). The suspension is stirred at 90oC for 2 hours in nitrogen atmosphere and treated. The residue is subjected to column chromatography on silica gel with elution with a mixture of methylene chloride and methanol, 99:1, and get named in the title compound (0.29 grams, 81,6%).

1H NMR (Dl3, TMS): 4,01 (6N, C) 4,07 (3H, m), 7,35 (1H, d, J=9.1 Hz), was 7.45 (1H, t, J=6.6 Hz).

Example 3

Synthesis of 5-chloro-4-(4-chloro-2-fluoro-5-(4,6-dimethoxy-2-triazinone)phenyl)-1-deformity-2-methylimidazole (compound 2-4) (method 3)

5-chloro-4-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-deformity-2-Mei (obtained by the method described in the patent EP 590834) (0.31 g, 1 Zin (0.21 g, 1.2 mmol), and the suspension is stirred at 110oC for 2 hours in nitrogen atmosphere. The mixture is treated, and the remainder chromatographic on silica gel with elution with a mixture of methylene chloride and methanol, 98: 2, and get named in the title compound (0.25 g, 55%).

1H NMR (CDCl3, TMS): 2,61 (3H, Ushs), 4,00 (6N, (C), 7,17 (1H, t, J=58,1 Hz), 7,29 (1H, d, J=9.3 Hz), 7,53 (1H, d, J=6,6 Hz).

Example 4

Synthesis of 1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -4-di-vermeil-3-methyl-1,4-dihydro-1,2,4-triazoline-5-on (compound 3-1) (method 4)

4.1

4-chloro-2-fluoro-5-(2-pyrimidinone)phenylhydrazone pyruvic acid

A solution of sodium nitrite (for 2.01 g) in water (15 ml) is added dropwise during 10 minutes to a cooled to -10oWith the solution of 2-(5-amino-2-chloro-4-pertenece)pyrimidine (7.0 g) in concentrated hydrochloric acid (40 ml) and stirred in a nitrogen atmosphere. Stirring is continued for 30 minutes at this temperature, and within 10 minutes, add a solution of chloride dihydrate tin (II) (16.3 g) in hydrochloric acid (20 ml). The resulting mixture is stirred for 2 hours at room temperature. Add water (20 ml) and add dropwise a solution of pyruvic acid (2.55 g) in water (10 ml). The resulting mixture is stirred for which the right) of the desired product.

4.2

1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -3-methyl-1,4-dihydro-1,2,4-triazoline-5-he

To a suspension of 4-chloro-2-fluoro-5-(2-pyrimidinone)phenylhydrazone pyruvic acid (1.24 g) in toluene (30 ml) at room temperature is added triethylamine (0.4 g). Add diphenylphosphinite (1,05 g), and the resulting mixture is refluxed for 1 hour. The solution process, and the remainder chromatographic on silica gel with elution by ethyl acetate, and receives a yellow solid (0.75 g).

4.3

1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -4-deformity-3-methyl-1,4-dihydro-1,2,4-triazoline-5-Oh (compound 3-1)

Gas Chlorodifluoromethane for several hours under stirring at room temperature bubbled to saturation through a solution of 1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -3-methyl-1,4-dihydro-1,2,4-triazoline-5-it (0,43 g) in tetrahydrofuran (100 ml). Add potassium hydroxide (0.4 g) and a catalytic amount of tetrabutylammonium, and the cooling bath removed. The mixture is stirred at room temperature for 48 hours. The solution process, and the oil obtained chromatographic on silica gel with elution with a mixture of ethyl acetate, hexane and methylene chloride, 1:2:2, and get a b the propylimidazolium-2,4-dione (compound 4-1) (method 5)

5.1

4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl-urea

A solution of 4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)-phenylisocyanate (1.3 g) in toluene (30 ml) is cooled to 5oWith, and through him bubbled ammonia gas for 15 minutes. Continue stirring for another 30 minutes, and the mixture is filtered, and the filtrate is evaporated, and receive a white solid (1.3 g).

1H NMR (Dl3): is 2.40 (3H, s), 7,20 (5H, m).

5.2

3-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -5-isopropylideneuridine-2,4-dione (compound 4-1)

A solution of 4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)-phenylacetone (1.24 g), ethyl-3-methyl-2-oxybutyrate (0.9 g) and p-toluensulfonate acid (0.1 g) in toluene (30 ml) is refluxed for 14 hours and treated, and receive a white solid (0.55 g), so pl. >220oC.

1H NMR (CDCl3): 1,90 (3H, s), is 2.30 (3H, s), 7,12 (1H, DD, J=5.7 Hz), 7,30 (1H, d, J=7 Hz), 7,40 (1H, d, J=9 Hz), 8,00 (1H, d, J=7 Hz), of 8.25 (1H, m), to 8.62 (1H, s).

Example 6

Synthesis of 2-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)-phenyl] -6,7-dihydropyrrolo[1,2-C] pyrimidine-1,3-(2H, 5H)-dione (compound 5-10) (method 6)

6.1

2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6,7-dihydropyrrolo[1,2-C]- the ml) stirred at 0oWith, and add dropwise a solution of triphosgene (13.8 g) in ethyl acetate (110 ml). The mixture is refluxed for 2 hours, cooled to room temperature, filtered, and the filtrate evaporated. The crude isocyanate was dissolved in N,N-dimethylformamide (70 ml) and added dropwise to a mixture of sodium hydride (1.2 g) and 2,2-dimethyl-5-(2-tetrahydropyrimidin)-1,3-dioxane-4,6-dione (9,9 g) in N,N-dimethylformamide (50 ml) under stirring at -30oC. the Mixture is stirred at room temperature for 0.5 hours and at 110oC for 4 hours. Reduce the volume under reduced pressure, and the residue is treated. Column chromatography (silica gel, hexane:ethyl acetate, 2:3) gives 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6,7-dihydropyrrolo[1,2-C] pyrimidine-1,3 (2H, 5H)-dione (9.0 g, 60%).

1H NMR (CDCl3, TMS): 1,36 (6N, d, J=6,1 Hz), 2,19 (2H, m) to 2.99 (2H, t, J=7.9 Hz), 3,99 (2H, m), 4,46 (1H, m), 5,74 (1H, s), 6,85 (1H, d, J=6.6 Hz), 7,29 (1H, d, J=6,6 Hz).

6.2

2-(4-chloro-2-fluoro-5-hydroxyphenyl)-6,7-dihydropyrrolo-[1,2-C] pyrimidine-1,3(2H,5H)-dione

This substance is synthesized from 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6,7-dihydropyrrolo[1,2-C]pyrimidine-1,3(2H,5H)-dione with a yield of 86% under the same conditions as described below to obtain 2-(4-chloro-2-fluoro-5-hydroxyphenyl)Gex), a 3.06 (2H, t, J=7.5 Hz), 3,13 (1H, ush), to 4.01 (2H, t, J=6.5 Hz), 5,71 (1H, s), 6.87 in (1H, t, J=6.9 Hz), 7,18 (1H, d, J=9,3 Hz).

6.3

2-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -6,7-dihydropyrrolo[1,2-C]pyrimidine-1,3(2H,5H)-dione (compound 5-10) (method 1)

This substance is synthesized from 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-6,7-dihydropyrrolo[1,2-C] pyrimidine-1,3(2H, 5H)-dione and 2-chloro-3-triptoreline with the release of 90% under the same conditions as described below to obtain 2-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl]hexahydro-3-thioxo-1H-[1,2,4]triazolo[1,2-a]pyridazin-1-it (example 10.3) (connection 8-29).

Example 7

Synthesis of 1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -4-(3-forproper)-1,4-dihydro-5-oxo-5H-tetrazole (connection 6-10) (mode 7)

7.1

1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -1,4-dihydro-5-oxo-5H-tetrazol

4-chloro-2-fluoro-5-(2-pyrimidinone)phenylisocyanate (0.96 g) and trimethylsilane (5 ml) is refluxed under nitrogen atmosphere overnight. The reaction mixture is treated, and the oil obtained chromatographic on silica gel with elution with a mixture of ethyl acetate and methylene chloride, 1:4, and receives a yellow semi-solid substance (0.54 g).

1H NMR (CDCl3, TMS): 7,16 (1H, DD, J=4,8 Hz), 7,49 (1H, d, J=9.3 Hz), to 7.64 (1H, d, J=6.8 Hz), 8,59 (2H, d, J=4,8 Hz)begins 6-10) (method 1)

A suspension of potassium carbonate (0.36 g), 1-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -1,4-dihydro-5-oxo-5H-tetrazole of 0.54 g) and 1-bromo-3-febraban (0,37 g) in N,N-dimethylformamide (10 ml) is stirred at an oil bath at 80oWith over 26 hours. The reaction mixture is treated, and the oil obtained chromatographic on silica gel with elution with a mixture of hexane and ethyl acetate, 2:1, and get the reaction product, so pl. 111-3oC.

1H NMR (Dl3, TMS): 2,30 (2H, m), 4,20 (2H, t, J=6.9 Hz), 4,59 (2H, dt, J= 46,9, and 6.6 Hz), 7,13 (1H, DD, J=4,8 Hz), of 7.48 (1H, d, J=9.3 Hz), 7,58 (1H, d, J=6.8 Hz), 8,58 (2H, d, J=4,8 Hz).

Example 8

Synthesis of 9-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino]-8-thia-1,6-diazabicyclo[4,3,0]nonan-7-she (compound 7-1) (method 8)

8.1

N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylenecarbonyl] -N1-formylhydrazine

Formic hydrazide (0.6 g) is added to a mixture of 4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylisothiocyanate (3.4 g) in tetrahydrofuran (20 ml) and the mixture is stirred for 3 hours at room temperature. The solvent is removed under reduced pressure, and the residue is treated. The oil obtained is dissolved in ethanol (30 ml), and add hexane to induce crystallization. Crystals otherthrow the si)phenylimino] -3-formyl-1,3,4-thiadiazolidine-2-he

To a solution of N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylenecarbonyl] -N1-formylhydrazine (2.8 g) in acetone (70 ml) under stirring at 0oWith add triphosgene (0.7 g) in toluene (20 ml). Stirring is continued at room temperature for 1 hour, and remove the solvents under reduced pressure. Column chromatography (methylene chloride: ethyl acetate, 3:1) gives the product of the reaction (3.3 grams).

8.3

5-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino] -1,3,4-thiadiazolidine-2-he

To a solution of 5-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino] -3-formyl-1,3,4-thiadiazolidine-2-she (3.3 grams) in acetone (60 ml) was added 10% solution of hydrogen chloride in methanol (8 ml). After stirring for 0.5 hours the solvents are removed under reduced pressure. Use the minimum amount of ethanol to dissolve the residue, and add hexane to induce crystallization. The crystals are filtered and dried, and get the reaction product (1.0 g, 36%).

8.4

9-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino] -8-thia-1,6-diazabicyclo[4,3,0]nonan-7-on (compound 7-1)

1,4-dibromobutane (0.64 g) is mixed with 5-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino] -1,3,4-thiadiazolidine-2-he shall owls, and the solvent evaporated. The residue is treated, and the oil obtained chromatographic (silica gel, hexane:ethyl acetate, 4: 1), and obtain the reaction product (0.65 g, 57%).

Example 9

Synthesis of 3-[4-chloro-2-fluoro-5-(trifluoromethyl-2-pyridyloxy)-phenyl] -1-ethylimidazolium-2,4-dione (compound 8-1) (way 9)

9.1

N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl]-2-chloracetamide

A solution of 2-(5-amino-2-chloro-4-pertenece)-3-triptoreline (1,32 g) and triethylamine (0.8 ml) in toluene (20 ml) stirred at 0oC, is added until the solution chloroacetanilide (0.4 ml) in toluene (10 ml). The mixture is stirred over night at room temperature and treated. Column chromatography on silica gel using as eluent the methylene chloride gives a white solid (1.4 g), so pl. 146-9oC.

1H NMR (Dl3, TMS): 4,20 (2H, s), 7,12 (1H, DD, J=5.8 Hz), 7,30 (1H, d, J=9 Hz), 8,01 (1H, m), by 8.22 (1H, m), a 8.34 (1H, d, J=7 Hz).

9.2

N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -2-ethylaminoethanol

A solution of N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl]-2-chloroacetamide (1.4 g) and 70% ethylamine (5 ml) in ethanol (25 ml) is refluxed for 3 hours and evaporated to dryness. The remainder of the OBR, Is, J=7 Hz), 3,39 (2H, s), 7,10 (1H, DD, J=6,8 Hz), 7,26 (1H, d, J=8 Hz), 8,00 (1H, m), 8,24 (1H, m), to 8.45 (1H, d, J=8 Hz), 9,86 (1H, s).

9.3

3-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -1-ethylimidazolium-2,4-dione (compound 8-1)

A solution of N-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl]-2-ethylaminoethanol (0,82 g) and 1,11-carbonyldiimidazole (0,43 g) in toluene (20 ml) is refluxed for 2 hours, cooled and treated. Column chromatography on silica gel with elution with 2.5% methanol in methylene chloride gives a yellowish-brown solid (0.8 g), so pl. 162-3oC.

1H NMR (CDCl3, TMC): 1,24 (3H, t, J=7 Hz), 3,53 (2N, K, J=7 Hz), of 4.05 (2H, s), 7,13 (1H, m), 7,30 (1H, d, J=7 Hz), 7,38 (1H, d, J=9 Hz), 8,01 (1H, m), 8,24 (1H, m).

Example 10

Synthesis of 2-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] hexahydro-3-thioxo-1H-[1,2,4]triazolo[1,2-a]pyridazin-1-she (connection 8-29) (method 10)

10.1

2-[4-chloro-2-fluoro-5-(isopropoxy)phenyl] hexahydro-3-thioxo-1H-[1,2,4] triazolo[1,2-a]pyridazin-1-he

A solution of 4-chloro-2-fluoro-5-isopropoxyaniline (12.1 g) and triethylamine (12.0 g) in ethyl acetate (120 ml) cooled to 0oC and mix until is added dropwise a solution of thiophosgene (6.8 g) in ethyl acetate (100 ml). The reaction mixture is boiled with obratnymi in benzene (70 ml) and treated with a solution of 1-ethoxycarbonylpyrimidine (9.5 g) in benzene (10 ml). After stirring for 3 hours the solvent is evaporated, and the residue is dissolved in m-xylene (250 ml) containing sodium acetate (1.6 g), and refluxed for 22 hours. The solvents are removed under reduced pressure, and the residue chromatographic (silica gel, hexane:ethyl acetate, 60:40), and get the reaction product (17,2 g, 81%).

1H NMR (CDCl3, TMS): to 1.37 (6H, d, J=7.8 Hz), a 1.96 (4H, m), 3,71 (2H, m), was 4.02 (2H, m), 4,47 (1H, m), to 6.95 (1H, d, J=6.4 Hz), 7,30 (1H, d, J=9.0 Hz).

10.2

2-(4-chloro-2-fluoro-5-hydroxyphenyl)hexahydro-3-thioxo-1H-[1,2,4]triazolo[1,2-a] pyridazin-1-he

To a solution of 2-[4-chloro-2-fluoro-5-(isopropoxy)phenyl] hexahydro-3-thioxo-1H-[1,2,4] triazolo[1,2-a] pyridazin-1-it (17,2 g) in methylene chloride (120 ml) under stirring at 0oWith added dropwise concentrated sulfuric acid (22 ml). The mixture is stirred at room temperature for 1 hour, and add water with ice (200 g). The aqueous phase is extracted with methylene chloride, and the combined organic phases, dried over sodium sulfate and chromatographic (silica gel, ethyl acetate), and get the reaction product (14.5 g, 96%).

1H NMR (CDCl3, TMS): of 1.84 (4H, m), 3,82 (4H, m), 7,06 (1H, d, J=6.5 Hz), 7,58 (1H, d, J=8,8 Hz), or 10.6 (1H, s).

10.3

2-[4-chloro-2-fluoro-5-(2-Piri is oxyphenyl)hexahydro-3-thioxo-1H-[1,2,4] triazolo[1,2-a]pyridazin-1-he (0.5 g) is mixed with 2-chloropyrimidine (1 equiv.) and potassium carbonate (2 equiv.) in dimethyl sulfoxide (20 ml), and the resulting mixture was stirred at 100oC for 1.5 hours and at room temperature over night. The mixture is treated, and the residue is subjected to column chromatography (silica gel, methylene chloride: ethyl acetate, 3:1), and obtain the reaction product (0.34 g, 55%).

1H NMR (CDCl3, TMS): 1,92 (4H, m), of 3.69 (2H, m) to 3.99 (2H, m), 7,05 (1H, m), 7,37 (1H, d, J=6.5 Hz), 7,39 (1H, d, J=9.0 Hz), 8,53 (2H, d, J=4,8 Hz).

Example 11

Synthesis of 2-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] hexahydro-3-thioxo-1H-[1,2,4] triazolo[1,2-a] pyridazin-1-she (connection 8-18) (method 11)

9-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenylimino] -8-thia-1,6-diazabicyclo[4,3,0] nonan-7-he (see example 8) (0.2 g) is mixed with methanol (18 ml), and added a catalytic amount of sodium methoxide. The mixture is refluxed for 0.5 hours, and remove the solvent under reduced pressure. Column chromatography (silica gel, hexane:ethyl acetate, 3:2) gives the reaction product (0.2 g, 100%).

Example 12

(R, S)-2-[4-Chloro-2-fluoro-5-(2-pyrimidinone)phenyl] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-47) (method 11)

To a solution of 4-chloro-2-fluoro-5-(2-pyrimidinone)aniline (0.4 g) and triethylamine (0.34 g) in dry ethyl acetate (10 ml) add tivosh the filtrate evaporated under reduced pressure. The residue is dissolved in dry ethyl acetate (10 ml), and add ethylpiperazine (in 0.288 g). The solution is refluxed for 1 hour and evaporated, and get a brown solid. This substance was purified using column chromatography with elution with dichloromethane, and get white crystals (0.35 g). So pl. 238-239oC.

Similarly receive the following compounds.

(R,S)-2-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl]hexahydrobenzo[1,5-a] pyridine-1,3-dione (compound 8-48).

(S)-2-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-49).

(S)-2-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] hexahydro-3-ticoporo[1,2-C]imidazol-1(1H)-he (connection 8-50).

(R, S)-2-(4-chloro-2-fluoro-5-phenoxyphenyl)hexahydro-3-toxoids[1,5-a] pyridin-1(5H)-he (connection 8-51).

(R, S)-2-[4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-52).

(R, S)-2-[4-chloro-5-(2-cianfrocca)-2-forfinal] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-53).

(R, S)-2-[4-chloro-2-fluoro-5-(2-pyrazinone)phenyl] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-54).

(R, S)-2-[4-chloro-5-(3-chloro-2-pyridyloxy)-2-fervency] -hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-56).

(R, S)-2-[4-chloro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-2-forfinal] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-57).

(R,S)-2-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)-phenyl]hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-58).

(R, S)-2-[4-chloro-2-fluoro-5-(3-nitropyridine)phenyl] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-59).

(R, S)-2-[4-chloro-5-(3-cyano-2-pyridyloxy)-2-forfinal]-hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-60).

Example 13

(R, S)-2-[5-(3-amino-2-pyridyloxy)-4-chloro-2-forfinal]-hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-61).

(R, S)-2-[4-chloro-2-fluoro-5-(3-nitropyridine)phenyl] hexahydro-3-toxoids[1,5-a] pyridin-1(5H)-he (0.21 g), dissolved in ethyl acetate (10 ml), restore in hydrogen atmosphere using a catalyst of palladium-on-coal (10%, 50 mg). After 5 hours stirring at room temperature the mixture is filtered, and the filtrate evaporated under reduced pressure. The residue is purified column chromatography with elution with a mixture of dichloromethane and et is)-4-chloro-2-forfinal] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-62).

Example 14

(R, S)-2-[5-(3-acetylamino-2-pyridyloxy)-4-chloro-2-forfinal] hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-63)

To a solution of (R,S)-2-[5-(3-amino-2-pyridyloxy)-4-chloro-2-forfinal]hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-she (0,22 g) and triethylamine (of 0.066 g) in dry ethyl acetate (10 ml) under stirring at 5oWith add acetylchloride (0,047 g). The solution is stirred for 1 hour at room temperature, filtered, and the filtrate evaporated. The residue is purified column chromatography with elution with a mixture of dichloromethane and ethyl acetate, 8:2, and obtain brown crystals (0.24 g).

Similarly receive

(R, S)-2-[5-[2-[(bis-benzoyl)amino] phenoxy]-4-chloro-2-feranil]hexahydro-3-toxoids[1,5-a]pyridin-1(5H)-he (connection 8-64).

Example 15

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-1)

15.1

Synthesis of 2-(5-amino-2-chloro-4-pertenece)-3-nitropyridine (intermediate compound IIA) (method 1)

A mixture of 5-amino-2-chloro-4-terfenol (0.64 g), powdered potassium hydroxide (0.24 g) and 2-chloro-3-nitropyridine (0,76 g) in dimethyl sulfoxide (15 ml) and heat at 110oWith stirring for 2 hours. Restgored, 3:97, and get 2-(5-amino-2-chloro-4-pertenece)-3-nitropyridine (intermediate compound IIA) as a yellow semi-solid substances (0.45 g).

Similarly receive the following compounds.

2-(5-amino-2-chloro-4-pertenece)-5-bromopyridin(intermediate compound IIb).

2-(5-amino-2-chloro-4-pertenece)-5-chloropyridin (intermediate compound IIc).

2-(5-amino-2-chloro-4-pertenece)-6-herperidin (intermediate compound (IId).

2-(5-amino-2-chloro-4-pertenece)-6-chloropyridin (intermediate compound IIE).

2-(5-amino-2-chloro-4-pertenece)-3,5,6-triptorelin (intermediate compound IIf).

2-(5-amino-2-chloro-4-pertenece)-3-triptorelin (intermediate compound IIg).

2-(5-amino-2-chloro-4-pertenece)-4-triptorelin (intermediate compound IIh).

2-(5-amino-2-chloro-4-pertenece)-3-cyanopyridine (intermediate compound IIi).

2-(5-amino-2-chloro-4-pertenece)-5-cyanopyridine (intermediate compound IIj).

2-(5-amino-2-chloro-4-pertenece)-5-nitropyridine (intermediate compound IIk).

2-(5-amino-2,4-divergence)-3-triptorelin (intermediate compound IIl).

2-(5-amino-2-chloro-4-forfeitability (intermediate compound IIn).

2-(5-amino-2-chloro-4-pertenece)pyridine (intermediate connection O).

15.2

Synthesis of 3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-1) (method 20)

The solution triphosgene (0,47 g) in ethyl acetate (10 ml) is stirred under nitrogen atmosphere until is added dropwise a solution of 2-(5-amino-2-chloro-4-pertenece)-3-nitropyridine (0.45 g) and triethylamine (0.45 ml) in ethyl acetate (15 ml). The mixture is refluxed for 2 hours, cooled, filtered, and the filtrate is evaporated, and receive the corresponding isocyanate.

A suspension of sodium hydride (0,038 g) in N,N-dimethylformamide (2 ml) was stirred at 0oIn nitrogen atmosphere, adding to it at this time dropwise a solution of ethyl-3-amino-4,4,4-trifurcation (0.26 g) in N,N-dimethylformamide (1 ml). After 15 minutes, add gradually a solution of the obtained isocyanate in N, N-dimethylformamide (5 ml) and toluene (5 ml) and the solution stirred overnight at room temperature. Add diluted hydrochloric acid, and the solution process. The obtained solid substance chromatographic on silica gel with elution with a mixture of methanol and methylene chloride, 5:95, and receive 3-[4-chloro-2-fluoro-5-(3-nitro-2-Piri is Gogo substances (0.32 g).

Similarly receive the following compounds.

3-[4-chloro-2-fluoro-5-(5-bromo-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-2).

3-[4-chloro-2-fluoro-5-(5-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-3).

3-[4-chloro-2-fluoro-5-(6-fluoro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-4).

3-[4-chloro-2-fluoro-5-(6-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-5).

3-[4-chloro-2-fluoro-5-(3,5,6-Cryptor-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-6).

3-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-7).

3-[4-chloro-2-fluoro-5-(4-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-8).

3-[4-chloro-2-fluoro-5-(3-cyano-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-9).

3-[4-chloro-2-fluoro-5-(5-cyano-2-pyridyloxy)phenyl] -6--2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-11).

3-[2,4-debtor-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-12).

3-[4-chloro-2-fluoro-5-(3-ethylsulfonyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-13).

3-[4-chloro-2-fluoro-5-(3-methyl-4-nitro-5-isothiazolinone)-phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-14).

3-[4-chloro-2-fluoro-5-(4-chloro-2-pyrimidinone)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-16).

3-[4-chloro-2-fluoro-5-(4,6-dimethoxy-2-pyrimidinone)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compound 11-17).

15.3

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-1) (method 15)

A suspension of potassium carbonate (0,23 g), 3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-Tetra-hydropyridine-2,4-dione (0.5 g) and 2,4-dinitrobenzamide (0.32 g) in N,N-dimethylformamide (10 ml) was stirred at room temperature overnight. The solution process, and the oil obtained chromatographic on silica gel with elution with a mixture of methanol and S="ptx2">

Similarly receive the following compounds.

1-amino-3-[4-chloro-2-fluoro-5-(5-bromo-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-2).

1-amino-3-[4-chloro-2-fluoro-5-(5-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-3).

1-amino-3-[4-chloro-2-fluoro-5-(6-fluoro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-4).

1-amino-3-[4-chloro-2-fluoro-5-(6-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-5).

1-amino-3-[4-chloro-2-fluoro-5-(3,5,6-Cryptor-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-6).

1-amino-3-[4-chloro-2-fluoro-5-(3-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-7).

1-amino-3-[4-chloro-2-fluoro-5-(4-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-8).

1-amino-3-[4-chloro-2-fluoro-5-(3-cyano-2-pyridyloxy)phenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-9).

1-amino-3-[4-chloro-2-fluoro-5-(5-cyano-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-on (connection 9-11).

1-amino-3-[2,4-debtor-5-(3-trifluoromethyl-2-pyridyloxy)-phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-12).

1-amino-3-[4-chloro-2-fluoro-5-(3-ethylsulfonyl-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-13).

1-amino-3-[4-chloro-2-fluoro-5-(3-methyl-4-nitrothiazol-5-yloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-14).

1-amino-3-[4-chloro-2-fluoro-5-(2-pyrimidinone)phenyl] -6-trifluoromethyl-l, 2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-16).

1-amino-3-[4-chloro-2-fluoro-5-(4-chloro-2-pyrimidinone)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-17).

1-amino-3-[4-chloro-2-fluoro-5-(4,6-dimethoxy-2-pyrimidinone)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-18).

Example 16

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-15) (method 16)

The solution triphosgene (0.5 g) in ethyl acetate (10 ml) is stirred under nitrogen atmosphere until is added dropwise a solution of 2-(5-amino-2-chloro-4-pertenece) pyridine (0.4 g) and triethylamine (0.5 ml) in ethyl acetate (20 ml), the mixture is refluxed for 2 hours, cooled, the filter is N,N-dimethylformamide (2 ml) was stirred at 0oIn nitrogen atmosphere, adding to it at this time dropwise a solution of ethyl-3-amino-4,4,4-trifurcation (0.32 g) in N,N-dimethylformamide (1 ml). After 15 minutes, slowly add a solution of the obtained isocyanate in N, N-dimethylformamide (5 ml) and toluene (5 ml). The solution was stirred at room temperature for 2 hours, and treated with a solution of 2,4-dinitrobenzamide (0,42 g) in N,N-dimethylformamide (4 ml). Stirring is continued for 3 days. The solution process, and get a solid substance that chromatographic on silica gel with elution with a mixture of methanol and methylene chloride, 5:95. Get named in the title compound as a yellow solid (0.3 g).

Similarly receive the following compounds.

1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-1).

1-amino-3-[4-chloro-2-fluoro-5-(5-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-3).

Example 17

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-21)

17.1

3-[4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetr iformity-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.2 g), 2-chloronitrobenzene (1.3 g) and potassium carbonate (1.4 g) in N,N-dimethylformamide (100 ml) is refluxed for 3 hours in nitrogen atmosphere. The resulting mixture was poured into water (200 ml) and acidified by addition of a small amount of concentrated hydrochloric acid. The solution is extracted with a mixed solvent (ethyl acetate: hexane, 1: 1, 400 ml) and the organic phase is dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure, and the residue chromatographic on silica gel with elution with a mixture of ethyl acetate and hexane, 1: 1, and receive 3-[4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-18) as an amorphous solid (1.0 g).

Similarly receive the following compounds.

3-[4-chloro-2-fluoro-5-(3-methylsulphonyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-19).

3-[4-chloro-2-fluoro-5-(3-isopropylphenyl-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-20).

3-[4-chloro-2-fluoro-5-(4-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate compounds is in-2,4-dione (intermediate connection 11-22).

3-[4-chloro-2-fluoro-5-(3-nitro-5-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-23).

3-[4-chloro-2-fluoro-5-(2-cianfrocca)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-33).

3-[4-chloro-2-fluoro-5-(2-cyano-3-pertenece)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-34).

17.2

1-amino-3-[4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-21) (method 15)

A suspension of 3-(4-chloro-2-fluoro-5-(2-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (1.0 g), potassium carbonate (0,37 g) and 2,4-dinitrobenzamide (0.54 g) in anhydrous N,N-dimethylformamide (20 ml) was stirred at room temperature for 20 hours. The solution process, and the oil obtained chromatographic on silica gel with elution with a mixture of methylene chloride, hexane and ethyl acetate, 2:3:0,5. The reaction product is crystallized from a mixture of methylene chloride, hexane and ethyl acetate, and receive a white solid (0.45 g).

Similarly receive the following compounds.

1-amino-3-[4-chloro-2-fluoro-5-(3-methylsulphonyl-2-pyridyloxy)phenyl] -6-trifter the-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-20).

1-amino-3-[4-chloro-2-fluoro-5-(4-nitro-2-triptoreline)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-22).

1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-5-triptoreline)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-23).

1-amino-3-[4-chloro-2-fluoro-5-(2-cianfrocca)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-30).

1-amino-3-[4-chloro-2-fluoro-5-(2-cyano-3-pertenece)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-31).

Example 18

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(2-triptoreline)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-24)

18.1

3-[4-chloro-2-fluoro-5-(4-amino-2-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connecting 11-24)

A suspension of 10% Pd/C and 3-[4-chloro-2-fluoro-5-(4-nitro-2-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (4.0 g) in ethyl acetate (100 ml) is stirred overnight in a hydrogen atmosphere. The mixture is filtered through celite, and the filtrate concentrated. The oil obtained chromatographic on silica gel with elution with a mixture of ethyl acetate and hexane, 1: 0,8. 3-[4-chloro-2-fluoro-5-(4-amino-2-triptoreline)phenylprop substances (3.3 grams).

Similarly receive the following compounds.

3-[4-chloro-2-fluoro-5-(4-aminophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-25).

3-[4-chloro-2-fluoro-5-(3-amino-5-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-26).

3-[4-chloro-2-fluoro-5-(2-aminophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-27).

18.2

3-[4-chloro-2-fluoro-5-(2-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-28)

3-[4-chloro-2-fluoro-5-(4-amino-2-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (3.0 g) dissolved in anhydrous N, N-dimethylformamide (10 ml) and added to a solution of tert-butylnitrite (1.28 g) in anhydrous N, N-dimethylformamide (40 ml), stored at 60-5oC in nitrogen atmosphere. The resulting mixture was stirred for 30 minutes at this temperature. The solution was poured into water and extracted with a mixture of ethyl acetate and hexane, 1: 1 (300 ml). The organic phase is washed with brine and dried over anhydrous sodium sulfate. After removal of solvent the residue chromatographic on silica gel with allergiaprobleemide-2,4-dione (intermediate connection 11-28) was isolated as an amorphous solid (1.64 g).

Similarly receive the following compounds.

3-[4-chloro-2-fluoro-5-(3-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-29).

3-[4-chloro-2-fluoro-5-phenoxyphenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-30).

18.3

1-amino-3-[4-chloro-2-fluoro-5-(2-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-24) (method 15)

A suspension of 3-[4-chloro-2-fluoro-5-(2-triptoreline)phenyl]-6-trifluoromethyl-3,2,3,4-tetrahydropyrimidine-2,4-dione (0.7 g), potassium carbonate (0.27 g) and 2,4-dinitrobenzamide (0.39 g) in anhydrous N,N-dimethylformamide (20 ml) was stirred at room temperature for 72 hours. The solution process, and the oil obtained chromatographic on silica gel with elution with a mixture of hexane and ethyl acetate, 4:1, containing 0.1% of triethylamine. The reaction product (compound 9-24) was isolated as a pale yellow amorphous solid (0.6 g).

Similarly receive the following compounds.

1-amino-3-[4-chloro-2-fluoro-5-(3-triptoreline)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-25).

1-amino-3-[4-chloro-2-the Synthesis of ethyl-2-[4-[2-chloro-2-fluoro-5-(1-amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-Dion-3-yl)phenoxy]-phenoxypropionate (connection 9-27)

19.1

3-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-31)

3-[4-chloro-2-fluoro-5-(4-aminophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (2.0 g) is mixed with hot 30% sulfuric acid (5 ml), and add ice water (5.0 g). The mixture is maintained at 10oWith while in the bottom part of the mixture under stirring gradually introduced a solution of sodium nitrite (0.45 g) in water (5 ml). After stirring for 10 minutes, add urea (0.1 g), then a solution of nitrate of copper (2) (18.0 g) in water (170 ml) and copper oxide (1) (0.7 g). The mixture is stirred for 10 minutes, extracted with diethyl ether (50 ml x 3) and dried over sodium sulfate. The crude product is purified column chromatography (hexane:ethyl acetate, 4;1), and obtain 3-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (intermediate connection 11-31) (1.0 g).

19.2

Ethyl-2-[4-[2-chloro-4-fluoro-5-(6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-Dion-3-yl)phenoxy]phenoxy]propionate (intermediate connection 11-32)

A solution of 3-[4-chloro-2-fluoro-5-(4-hydroxyphenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (1.0 g) butane-2-one (20 ml) is mixed with ethyl-2-bromopropionitrile and evaporated. The crude product chromatographic, and obtain ethyl-2-[4-[2-chloro-4-fluoro-5-(6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-Dion-3-yl)phenoxy]phenoxy]propionate (intermediate connection 11-32) (0,81 g).

19.3

Ethyl-2-[4-[2-chloro-4-fluoro-5-(1-amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-Dion-3-yl)phenoxy] phenoxy]propionate (compound 9-27) (method 15)

A suspension of ethyl-2-[4-[2-chloro-4-fluoro-5-(4-trifluoromethyl-1,2,3,6-tetrahydropyrimidin-2,6-dione-3-yl)phenoxy] phenoxy] -propionate (0,81 g), potassium carbonate (0.24 g) and 2,4-dinitrobenzamide (0.35 g) in anhydrous N,N-dimethylformamide (20 ml) was stirred at room temperature for 24 hours. The solution process, and the oil obtained chromatographic on silica gel with elution with a mixture of hexane and ethyl acetate, 4:1. The reaction product ethyl-2-[4-[2-chloro-4-fluoro-5-(1-amino-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-Dion-3-yl)phenoxy] phenoxy]propionate (compound 9-27) was isolated as a pale yellow amorphous solid substances (0.51 g).

Example 20

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(5-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydro-2-oxo-4-dioxopyrimidine (connection 9-28) (method 17)

A mixture of 1-amino-3-[4-chloro-2-fluoro-5-(5-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrido the refrigerator for 4 hours. The mixture is cooled, filtered, and the residue evaporated under reduced pressure. The oil obtained chromatographic on silica gel with elution with a mixture of ethyl acetate and hexane, 4:6, and receives a yellow viscous oil (0.18 g).

Similarly receive

1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidin-2-oxo-4-dioxopyrimidine (connection 9-29).

Example 21

Synthesis of 1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-1)

21.1

1-amino-3-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione

A suspension of sodium hydride (1.0 g, 60% in oil) in N,N-dimethylformamide (30 ml) stirred at 0oIn nitrogen atmosphere, while added dropwise a solution of ethyl-3-amino-4,4,4-trifurcation (4.5 g) in N,N-dimethylformamide (20 ml). After stirring for 15 minutes at -35oSlowly add a solution of 4-chloro-2-fluoro-5-isopropoxyaniline (5.6 g) in toluene (25 ml). The solution was stirred at room temperature for 2 hours and treated with a solution of 2,4-dinitrobenzamide (5.8 g) in N,N-dimethylformamide (20 ml). Stirring is continued for 3 days. Rest is dilatata and hexane, 1:5, containing 0.1% of triethylamine. 1-amino-3-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione obtained as white solids (5.3g).

21.2

1-amino-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione

To a solution of 1-amino-3-(4-chloro-2-fluoro-5-isopropoxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (4.5 g) in methylene chloride (50 ml), under stirring at 0oTo add concentrated sulfuric acid (3 ml). After 1 hour the mixture is diluted with water and worked up. The oily product chromatographic on silica gel with elution with a mixture of ethyl acetate and hexane, 2: 3, and get 1-amino-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione as a pale yellow amorphous solid (3.6 g).

1H NMR (CDCl3, TMS): 7,27 (1H, d, J=8,8 Hz), to 6.88 (1H, d, J=6.5 Hz), 6,28 (1H, s), 5,86 (1H, Ushs), br4.61 (2N, C).

21.3

1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-1) (method 14)

At room temperature is added sodium hydride (75 mg, 60% in oil) to a mixture of 1-amino-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-for cwds add water and the reaction mixture is worked up. Chromatography on silica gel with elution with a mixture of ethyl acetate and hexane, 1:2, gives compound 9-1 in the form of a yellow semi-solid substance (0.1 g).

Similarly receive the following compounds.

1-amino-3-[4-chloro-2-fluoro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-32).

1-amino-3-[2,4-dichloro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-33).

1-amino-3-[2,4-debtor-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-34).

1-amino-3-[4-chloro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-35).

1-amino-3-[4-bromo-2-fluoro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-36).

1-amino-3-[4-bromo-5-(5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-37).

1-amino-3-[4-chloro-2-fluoro-5-(3-amino-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-38).

1-amino-3-[4-chloro-2-fluoro-5-(3-amination the-3-[4-chloro-2-fluoro-5-(3-aminoacetyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-40).

1-amino-3-[4-chloro-2-fluoro-5-(3-aminomethanesulfonic-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-41).

1-amino-3-[4-chloro-2-fluoro-5-(3-chloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-42).

1-amino-3-[4-chloro-2-fluoro-5-(6-bromo-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-43).

1-amino-3-[4-chloro-2-fluoro-5-(3-chloro-3-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-44).

1-amino-3-[4-chloro-2-fluoro-5-(3-nitro-5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-45).

1-amino-3-[4-chloro-2-fluoro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-46).

1-amino-3-[4-chloro-2-fluoro-5-(3,5-dichloro-2-pyridyloxy)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-47).

1-amino-3-[4-chloro-2-fluoro-5-(3,5-dinitro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-48).

1-amino-3-[4-chloro-2-fluoro-5-(4,6-bistritei-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-49).

1-amino-3-[4-chloro-2-fluoro-5-(4,5-bistritei-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-51).

1-amino-3-[4-chloro-2-fluoro-5-(3,6-bistritei-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9 to 52).

1-amino-3-[4-chloro-2-fluoro-5-(3,5,6-trichloro-4-trifluoromethyl-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-53).

1-amino-3-[4-chloro-2-fluoro-5-(3,4,5-trichloro-6-trifluoromethyl-2-pyridyloxy)phenyl] -1-methyl-6-trifluoromethyl-2,4-(1H, 3H)-pyrimidinedione (connection 9-54).

1-amino-3-[4-chloro-2-fluoro-5-(3,5-dichloro-4,6-debtor-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-55).

1-amino-3-[4-chloro-2-fluoro-5-(3,5,6-Cryptor-4-bromo-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-56).

1-amino-3-[4-chloro-2-fluoro-5-(3,4,5,6-tetrachloro-2-pyridyloxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-57).

1-amino-3-[4-chloro-2-fluoro-5-(5-bromo-2-pyrimidinone)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-58).

1-amino-3-[4-chloro-2-fluoro-5-(6-chloro-5-nitro-4-pyrimidinone)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dihydropyrimidine-2,4-dione (compound 9-60).

1-amino-3-[4-chloro-2-fluoro-5-(2-chloro-6-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-61).

1-amino-3-[4-chloro-2-fluoro-5-(4-fluoro-6-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-62).

1-amino-3-[4-chloro-2-fluoro-5-(3-fluoro-6-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-63).

1-amino-3-[4-chloro-2-fluoro-5-(3-fluoro-2-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-64).

1-amino-3-[4-chloro-2-fluoro-5-(2-pertenece)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-65).

1-amino-3-[4-chloro-2-fluoro-5-(3-pertenece)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-66).

1-amino-3-[4-chloro-2-fluoro-5-(4-pertenece)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-67).

1-amino-3-[4-chloro-2-fluoro-5-(2-chloro-4-nitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-68).

1-amino-3-[4-chloro-2-fluoro-5-(4-cyano-2,3,5,6-tetraterpenes)phenyl] -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-69).

1-amino-3-[4-chloro-2-fluoro-5-(3-chloro-4,6-dinitrophenoxy)phenyl] -6-trifluoromethyl-1,2,3,4-then it is carbonated,3,4-tetrahydropyrimidine-2,4-dione (compound 9-71).

1-amino-3-[4-chloro-2-fluoro-5-(6-chloro-3-pyridazinyl)phenyl]-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (compound 9-72).

Some of the compounds of the present invention obtained by the methods described above, are shown in tables 1-9. Physical data on intermediate compounds, including NMR data are given in tables 10 and 11. Data of NMR for compounds of the present invention are given in the table. 12.

Compounds of the present invention find excellent herbicide action, when used as active ingredient (AI) of the herbicide. The herbicide may be used for wide applications, for example, on lands under cultivated plants, such as rice fields, dry land, land under fruit orchards and mulberry trees, and on land not occupied cultivated plants, such as forests, agricultural roads, playgrounds and places of industrial enterprises. You can find a suitable application method for application in the treatment of soil and nekorennogo application.

Compounds of the present invention is used to control noxious weeds, including grasses (gramineae), such as plushie PR is cjh (Avena fatua L), jonssonova grass (Sorghum halepense), quack grass (Agropyron repens), borovnik (Brachiaria piantaginea), millet purple (Panicum purpurascen), leptochloa (Leptochloa chinensis) and leptochloa red (Leptochloa panicea); sedges (or Senegalese), such as rice syt (rus iria L. ), purple nutsedge (Cyperus rotondus L.), reed Japanese (Scripus Juncoides), Cyperus (Cyperus serotinus), Cyperus long small-flowered (Cyperus difformis), thin bolotnitsa (Eleocharis acicularis) and water chestnut (Eleocharis kuroguwai); castucci, such as arrowhead broad-leaved Japanese (Sagittaria pygmaea), arrowheads (Sagittaria trifolia) and cistoca lanceolate (Alisma canaliculatum); pontedericeae, such as monochoria (Monochoria vaginalis) and monochoria species (Monochoria korsakovii); Nalichnaya, such as false bedrenets (Lindernia pyxidaria) and abunome (Dopatrium Junceum); lythraceae such as rotala Indian (Rotala indica) and red stem (Ammannia multiflora); and broad, such as amaranth paniculate (Amaranthus retroflexus), canetic Theophrastus (Abutilon theophrasti), morning glory (Ipomoea hederacea), white pigweed (Chenopodium album), breast prickly Sida spinosa L. ), garden purslane (Portulaca oleracea L.), thin amaranth (Amaranthus viridis L.), wall-cress (Cassia obtusifolia), black nightshade (Solanum nigrum L.), Highlander pepper (Polygonum lapathifolium L.), woodlouse (Stellaria media L.), common cocklebur (Xanthium strumarium L.), core wavy (Cardamine flexuosa WITH.), dead-nettle (Lamium amplexicaule L.) and Grushenka trancemania (Acalypha australis L.). Accordingly, they are useful for neumerous (Zea mays L.), soybean (Glycine max Merr. ), cotton (Gossypium species), wheat (Triticum), rice (Oryza sativa L.), barley (Hordeum vulgare L.), oats (Avena sativa L.), sorghum (Sorghum bicolor Moench), canola (Brassica napus L.), sunflower (Helianthus annuus L. ), sugar beet (Beta vulgaris L.), sugarcane (Saccharum officinarum L. ), Japanese lawn grass (Zoysia Japonica stend), peanut (Arachis hypogaea L.) and flax (Linum usitatissimum L.).

For use as herbicides, the active ingredients of the present invention is introduced into the composition of the herbicide compositions by mixing herbicide-active quantities of them with inert ingredients known in the art, to facilitate the suspension, dissolution or emulsification of the active ingredient for the desired application. The type of the resulting composition depending on the structure, culture and systems of application may affect the activity and usefulness of the active ingredient in practice. Thus, for use in agriculture herbicide compounds of the present invention can be manufactured in the form of dispersible granules, granules for direct soil, water soluble concentrates, wettable powders, Farrukh Dustov, solutions, concentrates, emulsions (SE), micro-emulsions, suspoemulsions, invert emulsion, or other types saimono to make on the identified area (where the suppression of unwanted vegetation is the goal) Farrukh Dustov, pellets or mixed with water or solvent compositions for spraying. Such compositions may contain the active ingredient from such a small amount as 0.1 wt.%, to such a large number as 97 wt.%.

Dusty represent a mixture of the active ingredient with pulverized materials, such as clay (some examples of compositions include kaolin and montmorillonite), talc, granite dust, or other organic or inorganic solids which act as dispersants and carriers for the active ingredient; these pulverized materials have an average particle size less than 50 microns. Typical gustova composition will contain 1% of the active ingredient and 99% of the media.

Wettable powders are composed of small particles, which rapidly disintegrate in water or other media formulations for spraying. Typical carriers are kaolin, mullerova earth, silica and other absorbent wettable inorganic materials. You can obtain wettable powders containing from 1 to 90% of active ingredient, depending on the desired patterns of use and absorbent capacity of the media. Moisten the other media.

Dispersible in water, the granules are granulated solid materials, which are easily dispersed when mixed with water. This composition usually consists of active ingredient (0,1%-95% of active ingredient), wetting agent (1-15 wt. %), dispersant (1-15 wt.%) and inert carrier (1-95 wt.%). Dispersible in water, the granules can be obtained by thoroughly mixing the ingredients and then adding a small amount of water on a rotating disk (specified mechanism available commercially) and collecting the agglomerated granules. On the other hand, the mixture of ingredients can be mixed with the optimal amount of liquid (water or other liquid) and pass through the extruder (the specified mechanism is available commercially) provided with holes, allowing you to get a small extruded pellets. On the other hand, the mixture of ingredients can be pelletized using a high speed mixer (specified mechanism available commercially) by adding small quantities of liquid and mixing at high speed for impact on agglomeration. On the other hand, the mixture of ingredients can be atomized in water and dried with a spray dispersion which is commercially available). After granulation, the moisture content is brought to an optimum level (usually less than 5%), and the product is screened to obtain particles of the desired size (mesh).

Granules are granulated solids, which do not disintegrate in water and retain its physical structure when introduced into the soil using a machine for making dry granular materials. Such granular solid materials can be obtained from clay, plant material, such as flour from rods corn cobs, agglomerated silica, or other agglomerated

organic or inorganic materials or compounds such as calcium sulfate. The composition consists, typically, of the active ingredient (1-20%), sprayed on or absorbed in granules. The granule can be obtained by thorough mixing of the active ingredient from the granules with or without addition of bonding agent to facilitate adhesion of the active ingredient to the surface of the granules, or by dissolving the active ingredient in a solvent, spraying the dissolved active ingredient and solvent, as pellets, followed by drying to remove solvent. Gr is ncentrate emulsions (EC) are homogeneous fluid consisting of a solvent or mixture of solvents, such as xylene, heavy ligroin shoulder straps, isophorone, or other proprietary commercial compositions derived from petroleum straps, the active ingredient and emulsifier or emulsifiers. For herbicide applications EC is added to water (or other carrier for the composition for spraying) and is applied in the form of a composition for spraying on the target square. The composition of the EC may contain 0.1 to 95% active ingredient, 5-95% solvent or mixture of solvents and 1-20% of the emulsifier or mixture of emulsifiers.

Composition of concentrated suspensions (also known as fluid suspensions) are liquid composition consisting of a fine suspension of the active ingredient in the carrier, typically in water or non-aqueous medium such as oil. The concentrated suspensions generally contain the active ingredient (5-50 wt. per cent), the media, wetting agent, dispersant, anti-freeze, a viscosity modifier and pH modifiers. For the application of the concentrated suspensions is usually diluted with water and razbrasivayutsya on the target square.

The concentrated solutions are solutions of the active ingredient (1-70%) in solvents that have sufficient restitutie solutions without other inert ingredients, such as wetting, additives to facilitate the correct application is usually introduced into the tank of the sprayer to mix before spraying.

Microemulsions are solutions comprising the active ingredient (1-30%), dissolved in surface-active substance or the emulsifier without adding solvents. To this composition is not added to other solvents. Microemulsions are particularly useful when you need Slobodana composition, as in the case of processing of grass near residential buildings.

Suspoemulsions are combinations of two active ingredients. One active ingredient is prepared in the form of a suspension concentrate (1-50% active ingredient), and the second active ingredient is prepared in the form of an emulsion concentrate (0.1 to 20%). The reason for obtaining this kind of composition consists in the impossibility of obtaining TBE first ingredient because of poor solubility in organic solvents. Suspoemulsions composition allows the combination of two active ingredients that are packaged in one container, thereby minimising packaging waste and create a more user-friendliness of the product.

Herbicide compounds of this izopet what brename, the plant growth regulators or other agricultural chemicals. Some additives for mixing in the spray tank, such as a binder, a means of facilitating penetration, wetting, surface-active substances, emulsifiers, moisturizers, and tools, protect from UV, can be added in an amount of from 0.01 to 5%, to enhance the biological activity, stability, wetting, spraying on the foliage or absorption of the active ingredients to the target area, or to increase educational opportunities, suspension, dispersion, re-dispersion, emulsion, increase resistance to UV or improvement of other physical or physico-chemical properties of the active ingredient in the spray tank, the spray system or on a scheduled area.

Examples of compositions of the present invention are shown in table. 17-22.

Examples test

Use conventional greenhouse screening system on herbicide activity to evaluate herbicide efficacy and safety for cultivated plants data of the test compounds. Six species of broadleaf weeds, including amaranth paniculate (Amaranthus retroflexus, AMARE), canetic Theophrastus (Abuti alinaitwe (Ambrosia artemisiifolia L., AMBEL), used as a test species. Also use four types of grass weeds, including the results of the analysis of green (Setaria viridis, SETVI), plushie millet (Echinochloa crusgalli, ECHCG), consawu grass (Sorghum halepense, SORHA) and creeping weed (Digitaria sanguinalis, DIGSA). In addition, in the test include three cultural types - corn field (Zea mays L., variety Dekalb 535, CORN), soybean (Glycine max L., grade Pella 86, SOY) and upland rice (Oryza species, grade Tebonnet, RICE).

The test example 1. Pre-emergence treatment.

All plants are grown in 10-cm plastic pots filled with a mixture of sandy and loamy soils. For pre-emergence testing of seeds sown per day to make the test connections. Immediately after making the test specimens pre-emergence treatment water from the soil surface to make the test materials. Subsequently, these samples poured from the pan.

All test compounds are dissolved in acetone and applied to test specimens in the volume of 187 l/ha Test materials contribute at the rate in the range from 125 g AI/ha to 1000 g AI/ha using a sprayer on tracks equipped with leveling tip flat torch TJ8001E. Plants put on the table, who had been the 40-45 cm below the tip. For submission of the test solution through the tip when it is moved mechanically (by means of the chain drive with electric control) over the tops of all the tested plants/pots, use compressed air. This introduction simulates a typical industrial introduction of herbicides in the field.

Example of test 2. Post-harvest testing.

When post-harvest testing include technical non-ionic surfactant (0.25 per cent, o/o) to enhance the wettability of the leaf surface of plants-targets when the consumption rate in the range from 63 g AI/ha to 1000 g AI/ha In the case of post-harvest testing seeds are sown for 8-21 day before testing, in order to apply the test substance appeared shoots and well-developed leaves. During the post-harvest application of plants of all types are typically on the development stage of 2-3 leaves. Samples for post-harvest trials always pour from the pan.

At 14 days after application of the test materials register evaluation of phytotoxicity. Use the rating scale 0-100, described earlier in "Research Methods in Weed Science, 2nd edition, B. Truelove, Ed., Southern Weed Science Society, Auburn University, Auburn, Alabama, 1977. In short, "0" corresponds Ocala is used to determine both efficacy against types of weeds, and the danger for the cultivated species. Results for herbicide action of various compounds of the present invention, which are presented under the numbers listed in table. 1-9, are given in table. 13 and 14. The results show a significant difference between the compounds as effective against weeds and selectivity in relation to the culture. For selected compounds see excellent activity against most species of weeds with minimal damage to at least one species of cultivated plants.

Compositions of the present invention can be used in mixture or in combination with other chemicals for agriculture, fertilizers or reducing phytotoxicity means. In this case, they can detect even the best action or activity. As other chemicals for agriculture can be mentioned, for example, herbicides, fungicides, antibiotics, plant hormones, insecticides or acaricides. In particular, using herbicide compositions containing the compounds of the present invention, used in a mixture or in combination with one or more active ingredients other herbicides, you can enhance herbicide activity,soedineniya of the present invention and an active ingredient of another herbicide can be entered in different compositions so, they can be mixed for use at the time of application, or they can be administered in a single composition. The present invention covers such herbicide composition.

The ratio of the components when mixing compounds of the present invention with the active ingredient other herbicides cannot be defined, since it varies depending on the time and method of application, weather conditions, soil type and type of composition. However, one active ingredient of another herbicide can be enabled usually in an amount of 0.01-100 mass parts of one mass part of the compounds of the present invention. In addition, the total dose of each active ingredient is usually from 1 to 10,000 g/ha, preferably from 5 to 500 g/ha Present invention covers such herbicide composition.

As the active ingredients of other herbicides may be mentioned the following (common names). Herbicide compositions containing the compounds of the present invention used in combination with other herbicides, can sometimes detect a synergistic effect.

1. Active ingredients, which are believed to exhibit herbicide action by the violation of steps APK is uproared (including free acids, their esters or salts), such as aromatic carboxylic acids, such as 2,3,6 TBA, dicamba, dichlobenil, type pyridines, such as picloram (including free acids and their salts), triclopyr or clopyralid, and others, such as naptalam, benazolin or chinkara.

2. Active ingredients, which are believed to exhibit herbicide action by inhibiting photosynthesis of plants, including ingredients type ureas, such as Diuron, linuron, Isoproturon, chlortoluron, metaventure, tebuthiuron or fluometuron, type triazines, such as Simazine, atrazine, cyanazine, TERBUTHYLAZINE, atraton, hexazinone, metribuzin, simetryn, ametrine is high, prometryn or deltamethrin, type orallow, such as bromacil, terbacil or lenacil, type anilides, such as propanil or cipromed, urethane type, such as swap desmedipham or phenmedipham, type hydroxybenzonitrile, such as bromoxynil or ioxynil, and others, such as peridot, bentazon and metasol.

3. The type of salts of Quaternary ammonium bases, such as paraquat, Diquat or difenzoquat, which are believed themselves become free radicals with the formation of active oxygen in the plant, and, thus, find quick gerbil what exploits inhibition of chlorophyll biosynthesis in plants and abnormal accumulation in plant photosynthetic organism peroxide, including ingredients type diphenyl ether, such as nitrogen, lactofen, acifluorfen, acifluorfen, fomesafen, bifenox or gametocytes, type cyclic amides, such as hartlin, flumioxazin or flamelurker, and others, such as oxadiazon, sulfentrazone or thidiazuron.

5. Active ingredients that are believed to detect herbicide action, characterized by the activity of etiolirovaniya through inhibition of chromogenesis of plants such as carotenoids, including ingredients type pyridazinones, such as norflurazon, ozone chloride or nettlerash, type pyrazoles, such as pyrazolate, paradoxien or benzien, and others, such as fluridone, floramon, diflufenican, methoxyphenol, glamazon, amitrol, sulcotrione or isoxaflutole.

6. Active ingredients that are believed to specifically affect crop plants, including ingredients type aryloksyfenoksypropionowe acids, such as dichloromethyl, piratenpartei, fluazifop, galaxytool, quizalofop, phenoxypropanol or chalifour, and type cyclohexanediones, such as alexidine, sethoxydim, clethodim or tralkoxydim.

7. Active and is of minislot in plants including the ingredients of the type of the sulfonylureas, such as chlorimuron, nicosulfuron, methylsulfonyl, triasulfuron, primisulfuron, tribenuronmethyl, chlorsulfuron, benzylbromide, sulfometuron, prosulfuron, halosulfuron, thifensulfuron, rimsulfuron, azimsulfuron, flazasulfuron, imazosulfuron, cycloaliphatic, flupyrsulfuron, type triazolopyrimidines, such as flumetsulam or metosulam, type imidazolinones, such as imazapyr, imazapyr, imazighen, imazamox, mazamet, imazamethabenz, type pyrimidinemethanol acid, such as parliamentary, esperimenti or perimenopausal, and others, such as glyphosate, glufosfamide, glyphosatetolerant or sulfosate.

8. Active ingredients that are believed to detect herbicide action, interfering with normal metabolism in the assimilation of inorganic nitrogen such as glufosinate, glufosinateammonium, phosphinotricin or bialaphos.

9. Active ingredients that are believed to detect herbicide action through inhibition of cytogenesis of plant cells, including ingredients type dinitroanilines, such as triparanol, oryzalin, named, type of carbamates, such as propham, chlorpropham, Barban and Azul, type of organophosphorus compounds, such as amiprophosmethyl or butamifos, and others, such as DCPA and dithiopyr.

10. Active ingredients that are believed to detect herbicide action through inhibition of protein synthesis in plant cells, including ingredients type acetanilides, such as alachlor, metolachlor, propachlor, acetochlor (including combination with additives for the safety of herbicides (safeners)) and dimethenamid.

11. The active ingredients of the type of impact, causing herbicide action is still unknown, including dithiocarbamate, such as thiobencarb, ARTS, diallate, triallate, molinet, pebulate, cycloset, butyl, vernolate or prosulfocarb, and mixed herbicides such as MSMA, DSMA, endothal, ethofumesate, sodium chlorate, pelargonia acid and focalin.

Examples of combinations with other herbicides (see table. 23-26).

(Note: the abbreviations of the names of the weeds taken from Composite List of Weeds, published by the American society for the study of weeds in 1989).

The following examples illustrate the use of combinations of compounds of this invention with the creatures of the CSOs, that the industrial composition of existing herbicides are added in an appropriate amount in the mixture for spraying before spraying.

These compounds may also find utility as desiatov, which are used as an aid in the harvesting of crops such as cotton and potatoes. Preliminary studies conducted in the greenhouse by spraying the foliage of potato plants with solutions containing various compounds claimed in this invention. Within 1 week after application see the death of leaf tissue in excess of 90% when the treatment is carried out with solutions containing from 100 g to 1000 g AI on ha similarly, in the processing plants of cotton observed 100% mortality of leaf tissue within 48 hours after application.

Example test 1.

Use of the greenhouse system screening bioassay for assessing defoliants ability of the test compounds.

As the study species used cotton (Gossyium hirsutum L.). Cotton seeds sown in 10-cm square plastic pots containing a mixture of sand: soil drainage:peat in the ratio 3:2:1. Removal of foliage otka included experimental material testing. The test material was or in the form of concentrates that can handle emulsion (EK), or in the form of a solution in acetone. Oil concentrate crops (1%) or non-ionic surfactant (0.25 per cent) are added to the spray solution. The sprayer was calibrated in such a way as to deliver the material in the volume of 93 l/ha, using the sprayer on tracks equipped with leveling tip flat torch TJ800 at a pressure of 40 psi.

After treatment, the pots were returned to the greenhouse, where they were watered and maintained in favourable growth conditions for two weeks.

Defoliant effect plants were visually evaluated by counting the number of fully opened leaves remaining on the plant, and calculate the percentage reduction of the number of fully opened leaves on the plant at the time of spraying.

The results of the evaluation on day 14 after treatment are summarized in table. 15.

Example of test 2.

Field trials were conducted on Mature cotton grown on 36" rows. Plants were treated in the period, when approximately 60% of the bolls were open, using a sprayer mounted on the truck the ionic surfactant in the amount of 0.25%. Defoliation was assessed on day 14 after treatment.

The results are summarized in table. 16.

1. The compound of formula (I) or its salt,

< / BR>
where X, Y independently is hydrogen, halogen;

Z is oxygen;

Q choose among

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
R1- halogen;

R2- R5independently is hydrogen, C1-6-alkyl or C1-6-halogenated and R3and R5together with the atoms to which they are attached, form a four-semiline substituted or unsubstituted ring; R6is hydrogen, C1-6-halogenated, C1-6-cianelli, C1-6-alkoxy-C1-6-alkyl;

A1and A2independently oxygen or sulfur;

In CH or N;

R7and R8each independently is hydrogen, C1-6-alkyl and R7and R8together with the atoms to which they are attached, form a four-semiline substituted or unsubstituted ring;

R9and R10is hydrogen;

AG - pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl, isothiazole or phenyl, or pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl, isothiazole or phenyl substituted with up to five substituents, independently selected among halogen atoms, C1-C6-alkyl, halogen-Cand C1-C6-alkylsulfonyl, C1-C6-alkylsulfonyl, di-C1-C6-alkylaminocarbonyl, cyano, nitro, amino, hydroxy, C1-C6-alkylsulfonamides,1-C6-alkoxycarbonyl-C1-C6-alkoxy,

WITH1-C6-alkoxycarbonyl, bisbenzimide, aminoacetyl, aminoterephthalate or amino-C1-C6-alkylsulfonate;

when Q - Q3or Q6substituted phenyl is excluded.

2. The compound or its salt under item 1, where X is fluorine, Y is chlorine, Z is oxygen, Q is selected among Q1- Q9and Ar is 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 5-amino-2-pyridyl, 3-dimethylaminoethyl-2-pyridyl, 3-methylsulphonyl-2-pyridyl, 3-isopropylphenyl-2-pyridyl, 6-chloro-3-trifluoromethyl-2-pyridyl, 3,5,6-cryptosporidial, 2 pirimidil, 4 pirimidil, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimatix is phenyl, 4-nitrophenyl, 4-AMINOPHENYL, 4-hydroxyphenyl, 4-methylsulfonylamino, 4-(1-ethoxycarbonylmethoxy)phenyl, 2-cyano-phenyl, 2-cyano-3-forfinal, 2-cyano-4-forfinal, 2-amino-4-(1-ethoxycarbonylmethoxy)phenyl, 2-cyano-4-nitrophenyl, 4-amino-2-cyanophenyl, 4-nitro-2-triptoreline, 4-amino-2-triptoreline, 4-acetylamino-2-triptoreline, 4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolin or 5-nitro-2-thiazolyl;

when Q - Q6substituted phenyl is excluded.

3. The method of obtaining the compounds of formula (I) under item 1 or its salts, where X, Y, Z, Q, R1- R8, A1, A2, And AG are listed in paragraph 1 values, including the interaction of the compounds of formula

< / BR>
with the compound of the formula Ar-Hal, where Hal is a halogen atom, in the presence of a base.

4. The method of obtaining the compounds of formula (I) under item 1 or its salt, having the formula (XXXIII)

< / BR>
where Q - Q9;

X, Y, Z, R9, R10and AG are listed in paragraph 1 values

including the interaction of the compounds of formula (XXXII)

< / BR>
with a derivative of hydrazine of the formula

< / BR>
5. The method of obtaining the compounds of formula (I) under item 1 or its salt, having the formula (XXXIII)

< / BR>
where Q is the Union of the formula (III)

< / BR>
with alkyl-3-amino-4,4,4-trifurcation in the presence of a base and quenching the reaction by the amination agent.

6. The method of obtaining the compounds of formula (XXXV)

< / BR>
or its salt,

where X, Y, Z and ar have the meanings specified in paragraph 1,

including the interaction of halogenosilanes formula (XXXVIII)

< / BR>
salt aryl - or heteroarylboronic connection.

7. The method of obtaining the compounds of formula (XXXII)

< / BR>
or its salt,

where X, Y, Z and Ar have the meanings specified in paragraph 1,

includes treatment of compounds of formula (XXXIX)

< / BR>
where alkyl is an alkyl group,

acidic compounds.

8. The method of obtaining the compounds of formula (XXXVI)

< / BR>
or its salt,

where X, Y, Z, R9and R10have the values listed in paragraph 1,

including the interaction of the compounds of formula (XL)

< / BR>
with a derivative of hydrazine.

9. The method of obtaining the compounds of formula (I) under item 1 or its salt, having the formula (XXXIII)

< / BR>
where Q - Q9where R9and R10is hydrogen, A1and a2oxygen;

X, Y, Z and ar have the meanings specified in paragraph 1,

including the interaction of isocyanate of the formula (III)

< / BR>
with hydrazonium formula (XLI is th number of connection p. 1 and used in agriculture adjuvant.

11. Method of controlling weeds comprising applying to the locus, which protects, herbicide, characterized in that as herbicide use connections on p. 1 in an effective amount.

12. The method according to p. 11, characterized in that the protected locus is a field occupied by cereals.

13. The method according to p. 11, characterized in that the protected locus is a field occupied by soy.

14. The method according to p. 11, characterized in that it comprises applying effective amounts of the compounds under item 1 in combination with another herbicide to provide additive or synergistic herbicide action.

15. Method of weed control on p. 11, characterized in that the connection on p. 1 applied to the soil as prevschatuyu herbicide.

16. Method of weed control on p. 11, characterized in that the connection on p. 1 treated foliage plants.

17. Method of weed control on p. 11, characterized in that another herbicide is acetanilide, a sulfonylurea, or any other selected from phenoxyalkanoic acid, aromatic carboxylic acid, pyridine, urea, triazine, uracil, anilide, carbama is a, of pyrazole, aryloksyfenoksypropionowe acid, cyclohexanedione, sulfonylureas, triazolopyrimidine, imidazolinone, pyrimidinemethanol acid, dinitroaniline, amide, organophosphorus compounds, acetanilide, dithiocarbamates.

18. The way the desiccation of plants, including processing plants connection on p. 1.

19. The way the desiccation of plants under item 18, characterized in that the plant, which handles the connection is potatoes or cotton.

20. The connection formulas

< / BR>
where X, Y is hydrogen, halogen;

Z is oxygen;

AG has the same meaning as defined in paragraph 1;

A - hydrogen, -CS -,

or its salt.

21. The compound or its salt according to p. 20, where AG represents 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 6-amino-2-pyridyl, 3-dimethylaminoethyl-2-pyridyl, 3-methylsulphonyl-2-pyridyl, 3-Isopropenyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimethoxy-2-pyrimidyl, 2,6-dimethoxy-4-pyrimidyl, 4,6-dimethoxy-2-triazinyl, phenyl, 2-iopener, 2-trifloromethyl, 2-nitrophenyl, 4-nitrophenyl, 4-AMINOPHENYL, 4-hydroxyphenyl, 4-methylsulfonylamino, 4-(3-ethoxycarbonylmethoxy)phenyl, 2-cyanophenyl, 2-cyano-3-forfinal, 2-cyano-4-forfinal, 2-amino-4-(1-ethoxycarbonylmethoxy)phenyl, 2-cyano-4-nitrophenyl, 4-amino-2-cyanophenyl, 4-nitro-2-Cryptor-were, 4-amino-2-triptoreline, 4-acetylamino-2-triptoreline, 4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylmethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolin or 5-nitro-2-thiazolyl.

Priority points:

14.03.1997 on PP. 4-9;

26.08.1997 on PP. 20 and 21;

14.01.1998 on PP. 1-3, 10-19.

 

Same patents:

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- aminohydroxylation and carboxylic acid" target="_blank">

The invention relates to new compounds of General formula I, where Q, A, R1n, m are listed in the value formula

The invention relates to a derivative of 7- (alkoxycarbonyl-substituted) -10-hydroxy-taxan following formula 3b:

< / BR>
in which R1, R2, R4, R5, R6and R14defined above

The invention relates to new derivatives of carboxylic acids of General formula I containing heterocyclic ring
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