Method for pesticide production

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to method for production of compounds of general formula I wherein R1 represents CN or CSNH2; X represents N or C each R2 and R4 are independently hydrogen or chlorine; R3 represents halogen, haloalkyl, haloalkoxy or SF3; R5 and R6 are independently alkyl; n = 0, 1 or 2. Claimed method includes reaction of compound of formula II , wherein substituents are as defined above; W represent hydrogen, with metal inorganic salt or organic amine to form salt of compound II as intermediate and further reaction of said salt with alkylating agent of formula III wherein R6 is as defined above; Y represents leaving group. In another embodiment compounds of formula I are obtained by reaction of metal inorganic salt or organic base of formula II with abovementioned alkylating agent of formula III.

EFFECT: essentially decreased formation of side products; target products of high purity.

37 cl, 4 ex

 

The present invention relates to a process for the preparation of substituted pyrazoles and their use as pesticides.

Such pyrazoles as 5-amino-1-aryl-3-canoperate and its derivatives, such as fipronil (Fipronil), constitute an important class of insecticides. As described in WO 00/35884 and U.S. Patent No. 5556873, some substituted 5-N-alkyl-N-alkoxyamino-1-aryl-3-cyanopyridine have valuable pesticidal properties.

In U.S. Patent No. 4931461 disclosed substituted 5-methylamino-1-arylpyrazole and their use as tools for pest control. Considering substituted compounds can be obtained by different methods, but how it was discovered, the main way of obtaining them is the reaction of pyrazole with an alkylating agent. This method of getting being effective enough, leads to the formation of side products, which should be separated from the desired pesticide compounds.

The authors of the present invention have discovered an alternative way of obtaining the above mentioned compounds, which provides a reduced formation of by-products or completely eliminate their presence, thus eliminating the need for purification of the final product.

Accordingly, the present invention provides a method

(A) obtaining compounds of formula (I)

in which

R1represents CN or CSNH2;

X represents N or CR4;

each of the radicals R2and R4independently, represents a hydrogen or chlorine;

R3represents halogen, halogenated, halogenoalkane or SF5;

each of the radicals R5and R6independently, represents an alkyl group; and

n is 0, 1 or 2;

which includes the interaction of the compounds of formula (II):

in which the various symbols have the above values, and W is H with an alkylating agent of the formula (III):

in which R6has the above meaning and Y represents a leaving group.

The advantage of this method over known is that it is more efficient and provides more direct way of formation of the final product.

It was also found that before the interaction of the compound (II) with an alkylating agent can be pre-reaction of the compound (II) with an inorganic salt of the metal or organic base, resulting in the formation of the intermediate salt, which then reacts with the alkylating agent.

Thus, in accordance with the second aspect of the present invention, it is proposed a method (A) for obtaining the compounds of formula (I)

in which:

R1represents CN or CSNH2;

X represents N or CR4;

each of the radicals R2and R4independently, represents a hydrogen or chlorine;

R3represents halogen, halogenated, halogenoalkane or SF5;

each of the radicals R5and R6independently, represents an alkyl group; and

n is 0, 1 or 2;

which includes (a) the first stage of the interaction between the compounds of formula (II):

in which the various symbols have the values indicated above, and W represents H, an inorganic metal salt or organic base with the formation of intermediate compounds, (b) the second stage of the interaction between the intermediate obtained in stage (a)with an alkylating agent,

in which R6has the above meanings and Y represents a leaving group.

The advantage of the method of the present invention over known methods is that during the reaction does not generate secondary products, and the specified intermediate connection, if desirable, can be obtained and allocated. It was found that the intermediate connection is persistent.

In addition, the intermediate compound obtained in the way described above, not only is no new connection and thereby defines another aspect of the present invention.

The method of the present invention involves reacting compounds of General formula (II) with an alkylating agent or an optional preliminary stage in which first by reaction with an inorganic salt or an organic base, and then with an alkylating agent. Deputy R3in compound II may represent halogen, halogenated, halogenoalkane or SF5. If R3is halogenated, suitable halogenation can be halogenmethyl, in particular trifluoromethyl. If R3is halogenoalkane the best of halogenoalkane groups include halogenerators group, in particular triptoreline. Deputy R5represents an alkyl group, for example methyl, ethyl or propyl, in particular ethyl.

Preferably the substituents in the compound of General formula (II) have the following meanings:

R1is CN;

X represents CR4;

Each of R2and R4is chlorine;

R3represents trifluoromethyl;

R5represents ethyl;

W is N; and n is 1.

When interacting compounds of General formula (II) with a suitable alkylating agent alkylating agents can be selected from alkyl sulphonates, alkylhalogenide or alkyl sulphates. Alkyl the second group may represent methyl, ethyl, propyl or isopropyl. If the alkylating agent is a halide, the preferred agent is a chloride, bromide or iodide. If the alkylating agent is a sulfonate, it is preferable to use dimethylsulfone or mediarelations. When the alkylating agent is sulfate, the preferred sulfate is dimethylsulfate. The preferred alkylating agent is methyl bromide, modesty methyl or their salts, as well as dimethylsulfate.

The compound of General formula (II) is reacted with an alkylating agent in an amount up to 10 equivalents, preferably 1 to 20, particularly preferably 5 to 10 equivalents.

The reaction between the compound (II) and the alkylating agent can also be carried out in the presence of a base. Suitable bases include hydrides of alkali metals, such as sodium hydride; carbonates of alkali metals such as potassium carbonate or sodium carbonate, or bicarbonate; alkoxides of alkali metals such as sodium methoxide; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. On the other hand, consider the reaction can be carried out in the presence of such organic bases as pyridine or triethylamine; or Quaternary ammonium salt such as the halide of benzyltriethylammonium, for example, chloride or bromide, is whether salt R 4NOH, R4The NO, for example Bu4NOH. Preferred basic agents are potassium carbonate or potassium hydroxide.

Consider the reaction can also be carried out in the presence of a solvent, preferably a polar organic solvent which may be selected from ethers, such as tetrahydrofuran, tert-butyl methyl ether, dioxane, diisopropyl ether and disutility ether; halogen-substituted aromatic or aliphatic hydrocarbons, such as dichloromethane, 1,2-dichloroethane and monochlorobenzene; polar NITRILES and amides, such as acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. Preferred solvents are acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. There may also be present such non-polar solvents like toluene. Usually use the excess solvent.

In the case when the compound of General formula (II) initially interacts with an organic base or inorganic salt of the metal, as you can use a salt of the metal of group I or II selected from cesium, potassium, sodium, calcium and magnesium. The preferred salt of the metal salt is potassium or sodium. This salt can be used in aqueous solution or solid substances may be a hydroxide, carbonate or bicarbonate. In ka is este preferred salt in the method of the present invention using potassium carbonate or potassium hydroxide. As organic bases can be used amine, such as triethylamine, pyridine, etc.

The amount of compounds of General formula (II)interacting with the metal salt or organic base is at least 1 gram-equivalent, preferably 2 grams equivalent.

The first step for intermediate compounds can be carried out in the presence of a solvent, preferably a polar organic solvent which may be selected from ethers, such as tetrahydrofuran, tert-butyl methyl ether, dioxane, diisopropyl ether and disutility ether; halogen-substituted aromatic or aliphatic hydrocarbons, such as dichloromethane, 1,2-dichloroethane and monochlorobenzene; such polar NITRILES and amides, such as acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone, or mixtures thereof. The preferred solvent is acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. There may also be present such non-polar solvent like toluene. It is preferable to conduct the reaction in an excess of solvent.

The obtained intermediate product is a new substance and, thus, represents another aspect of the present invention. In particular this applies to those cases where the compound of General formula II interacts with the carbonate is Aliya with the formation of the potassium salt or triethylamine with the formation of the amine salt.

Then conduct the reaction of the intermediate with an alkylating agent of the formula (III). Such alkylating agent may be selected from alkyl sulphonates, alkylhalogenide or alkyl sulphates. Alcalina group in these compounds may represent methyl, ethyl, propyl or isopropyl. In the case when the alkylating agent is a halide compound, the preferred agent is a chloride, bromide or iodide. If the alkylating agent is a sulfonate, it is preferable to use dimethylsulfone or mediarelations. If the alkylating agent is a sulfate, the preferred sulfate is dimethylsulfate. The preferred alkylating agent is a methyl bromide, modesty methyl or their salts, as well as dimethylsulfate.

The amount of alkylating agent relative to the intermediate metal salt is up to 10 gram equivalents, preferably 1-20, especially 5-10 gram-equivalents.

The second stage of this method can also be carried out in the presence of a base. Suitable for use in the second stage of the Foundation include hydrides of alkali metals, such as sodium hydride; carbonates of alkali metals such as potassium carbonate or sodium carbonate, or bicarbonate; alkoxides of alkali metals, nab the emer sodium methoxide; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. On the other hand, the second stage can be carried out in the presence of such organic bases as pyridine or triethylamine; or a Quaternary ammonium salt as the halide of benzyltriethylammonium, for example, chloride or bromide, or salt R4NOH, R4The NO, for example Bu4NOH. The preferred base is potassium carbonate or potassium hydroxide.

The second stage reactions can also be carried out in the presence of a solvent, preferably a polar organic solvent which may be selected from such ethers like tetrahydrofuran, tert-butyl methyl ether, dioxane, diisopropyl ether and disutility ether; halogen-substituted aromatic or aliphatic hydrocarbons, such as dichloromethane, 1,2-dichloroethane and chlorobenzene; polar NITRILES and amides, such as acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. The preferred solvent is acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. There may also be present such non-polar solvent like toluene. It is preferable to use an excess of solvent.

The method according to the present invention can be performed at a temperature in the range from 0 to 150°C, preferably from to 90° C, at atmospheric or increased pressure.

The method of the present invention is particularly preferable for obtaining the compounds of General formula (I)in which:

R1is CN;

X represents CR4;

Each of R2and R4is chlorine;

R3represents trifluoromethyl;

R5represents ethyl;

R6is methyl; and n is 1.

The compounds of formula (II) can be obtained by the method (B), in which the compound of formula (IV):

where the various symbols have the above meanings, is reacted with allermuir agent of the formula (V) or formula (VI):

where R5has the above meanings and Y represents a halogen, especially chlorine or bromine; alkoxy, anhydride, especially haloganated, for example the acid chloride, and Z represents a halogen atom such as chlorine, bromine and iodine.

In a preferred compound of formula (V) R5is ethyl, and Y represents a chlorine atom, and preferred is the compound (VI) Z and Y represent chlorine atom.

Method (C) is preferably carried out in the presence of a solvent, preferably a polar organic solvent which may be selected from ethers, such as tetrahydrofuran, tert-butyl methyl ether, dioxane, diisopropyl the ether and di-tert-butyl ether; halogen-substituted aromatic or aliphatic hydrocarbons, such as dichloromethane, 1,2-dichloroethane and chlorobenzene; polar NITRILES and amides, such as acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone, or mixtures thereof. The preferred solvent is acetonitrile, N,N-dimethylformamide and N-methylpyrrolidinone. There may also be present such non-polar solvent like toluene. It is desirable that the solvent used in excess.

Method (C) can also be carried out in the presence of organic or inorganic bases. Suitable for this purpose includes hydrides of alkali metals, such as sodium hydride; carbonates of alkali metals such as potassium carbonate or sodium carbonate or bicarbonate; alkoxides of alkali metals such as sodium methoxide; hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide. On the other hand, consider the reaction can be carried out in the presence of organic base such as pyridine or triethylamine; or Quaternary ammonium salts such as halide of benzyltriethylammonium, for example, chloride or bromide, or salts R4NOH, R4The NO, for example Bu4NOH. The preferred base is potassium hydroxide, sodium hydroxide and triethylamine. Usually, the reaction is carried out at a temperature in inter the ale from minus 20° With up to 150°C, preferably at from 20° to 90°C.

In accordance with the private embodiment of the present invention, when using the compound (VI) to obtain the compound (II) in the case where each of the substituents Z and Y represent chlorine, the reaction of the considered compounds is carried out in the presence of a metal alkoxide, such as ethoxide sodium.

Compounds of formula (III), (IV) and (V)and (VI) are known or can be obtained by known methods.

The intermediate salt of compound (II) can also be obtained directly from the intermediate reaction medium of the compound (IV) with compound (V), discussed above. The allocation of such salts can be accomplished by filtration or by adding any suitable solvent.

Further, the present invention is illustrated by the following examples.

Example 1

Stage 1. Obtaining potassium salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole.

30 g ethoxyacetylene (0,233 mol) was added to a mixture of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-aminopyrazole (66 g, 0,145 mol) and triethylamine (44.5 kg city, 0,435 mol) in 100 ml of tetrahydrofuran.

The reaction mixture was stirred for 5 hours at 30°C, allowed to cool and was added 150 ml of water and 50 ml of CH 2Cl2. the pH of the mixture was restored to pH 2 using concentrated hydrochloric acid and the reaction product was extracted with CH2Cl2. Solution was added potassium carbonate (50%) and the resulting precipitate was concentrated, obtaining the compound II in which W represents potassium (yield=65%, purity=77%).

Stage 2. Obtain 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetylene)pyrazole.

To a suspension of the potassium salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole obtained in stage 1 (18,9 g, purity 75,6%, was 0.026 mol) of 56.8 g of acetonitrile was added a solution of bromide in acetonitrile (86,5 g, concentration of 28%, 0,255 mol). The resulting mixture was stirred for 6 hours at 60°and then concentrated to dryness. The residue was dissolved in a mixture of toluene (100 g) and water (100 g). The organic layer was washed with 100 g of water and concentrated to 38% solution, was heated up to 80°and the resulting product was recrystallized in toluene/n-heptane, taken in the ratio of 40/60, with the formation of 10.3 g of white solid (yield=64%, purity=85%).

Example 2

Stage 1. Getting the tea salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole.

of 3.32 g of chloride of ataxia is stated (0.03 mol) was added to a mixture of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-aminopyrazole (a total of 8.74 g, 0.02 mol) and triethylamine (8,4 ml, 0.06 mol) in 20 ml of tetrahydrofuran. The reaction mixture was stirred at 60°C for 1 hour and was added 1.1 g (0.01 mmol) of chloride ethoxyacetic. After stirring for 30 minutes the reaction mixture was allowed to cool and was added 20 ml of water and 20 ml of CH2Cl2. The organic layer was washed with 10 ml water and dried over magnesium sulfate. Received 12.5 g of compound (II) in which W represents triethylamine, which corresponded to a yield of 90% at a purity of 76%.

Stage 2. 0.42 mol triethylamine salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole obtained in stage 1, was dissolved in 5 ml of CH2Cl2. The system was acidified with hydrochloric acid to pH 2, and separated the organic layer. Then the resulting organic layer was treated with concentrated NaOH solution (1.5 equivalent) and iodine stands (1.5 equivalent) to obtain the compound I with the release of 40%.

Example 3

Stage 1. 3.1 g of chloride ethoxyacetic (0,024 mol) for 2 hours was added to a mixture of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-aminopyrazole (10 g, of 0.022 mol) and KOH (3.2 g, of 0.57 mol) in 7 g of CH3CN. The reaction mixture was stirred for 2 hours at -5°and the resulting mixture was filtered, resulting in a received 15 g of wet Tverdov the material. After drying was obtained 12.2 g of compound (II) in which W represents potassium (yield=87%, purity 82%).

Stage 2. Obtain 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetylene)pyrazole.

To a suspension of the potassium salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole, (0,251 g, purity 82%, 0.36 mol) in 1,3 g of acetonitrile was added a solution of methyl bromide in acetonitrile (0.7 g, concentration of 28%, 2.1 mol). The resulting mixture was stirred for 6 hours at 60°in the autoclave. The chemical yield of the final product was 85%.

Example 4

Carried out the reaction between 1 equivalent of fipronil and 0.65 equivalents of chloride ethoxyacetic in the environment of tetrahydrofuran and in the presence of 3 equivalents of triethylamine and trace amounts of 4-dimethylaminopyridine with 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-ethoxyacetic-4-triftormetilfullerenov with a yield of 75% (based on acetyl chloride.

Then the resulting product for 4 hours at 25°were treated With an equivalent amount of dimethylsulfate and an equivalent amount of potassium carbonate in an environment of tetrahydrofuran to form a 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-N-ethoxyacetic-N-methyl-4-triftormetilfullerenov.

p> 1. The method of obtaining compounds of General formula (I)

in which

R1represents CN or CSNH2;

X represents N or CR4;

each of the radicals R2and R4independently from each other, represents a hydrogen or chlorine;

R3represents halogen, halogenated, halogenoalkane or SF5;

each of the radicals R5and R6independently from each other, represents an alkyl group;

n is 0,1 or 2;

moreover, consider the method includes the following stages:

a) interaction of the compounds of formula (II):

in which R1, R2, R3, X, R5and n have the above values, and W represents H, an inorganic metal salt or organic base with the formation of salts of the compounds of formula (II) as an intermediate connection;

b) interaction of the indicated salts of the compounds of formula (II) with an alkylating agent of the formula (III):

in which R6has the above value, a Y is a leaving group.

2. The method of obtaining the compounds of formula (I):

in Kotor is th R 1represents CN or CSNH2;

X represents N or CR4;

each of the radicals R2and R4independently from each other, represents a hydrogen or chlorine;

R3represents halogen, halogenated, halogenoalkane or SF5;

each of the radicals R5and R6independently from each other, represents an alkyl group;

n is 0,1 or 2;

which includes the interaction of the inorganic metal salt or organic salts of the compounds of formula (II):

in which R1, R2, R3, X, R5and n have the above values, a W is N, with alkiliruushim agent of formula (III):

in which R6has the above value, a Y is a leaving group.

3. The method according to claim 2, in which the alkylating agent is an alkyl halide, alkylsulfonate or alkylsulfate.

4. The method according to claim 1 in which the alkylating agent is an alkyl halide, alkyl sulphonates or alkylsulfate.

5. The method according to claim 3, in which the alkylating agent is a methyl bromide, methyl iodide or dimethylsulfate.

6. The method according to claim 4, in which the alkylating agent is bromothymol, methyl iodide or dimethylsulfate.

7. The method according to claim 1, wherein the reaction is carried out in the presence of a solvent.

8. The method according to claim 2, in which the reaction is carried out in the presence of a solvent.

9. The method according to claim 3, in which the reaction is carried out in the presence of a solvent.

10. The method according to claim 4, in which the reaction is carried out in the presence of a solvent.

11. The method according to claim 1, in which stage 1 and 2 is carried out in the presence of a base.

12. The method according to claim 3, in which the reaction is carried out in the presence of a base.

13. The method according to claim 6, in which stages 1 and 2 is carried out in the presence of a base.

14. The method according to claim 7, in which the reaction is carried out in the presence of a base.

15. The method according to claim 1, wherein the inorganic metal salt is a salt of a metal of group I or II selected from cesium, potassium, sodium, magnesium and calcium.

16. The method according to claim 3, in which the inorganic salt of the metal compounds of the formula (II) is a salt of a metal of group I or II selected from cesium, potassium, sodium, magnesium and calcium.

17. The method according to claim 6, in which the inorganic metal salt is a salt of a metal of group I or II selected from cesium, potassium, sodium, magnesium and calcium.

18. The method according to claim 7, in which the inorganic salt of the metal compounds of the formula (II) is a salt of a metal of group I or II selected from cesium, potassium, sodium, magnesium and calcium.

20. The method according to item 15, in which inorganic salts are the hydroxide, carbonate or bicarbonate.

21. The method according to clause 16, in which inorganic salts are the hydroxide, carbonate or bicarbonate.

22. The method according to item 15, in which the inorganic salt is a potassium carbonate or potassium hydroxide.

23. The method according to clause 16, in which the inorganic salt is a potassium carbonate or potassium hydroxide.

24. The method according to 17, in which the inorganic salt is a potassium carbonate or potassium hydroxide.

25. The method according to p, in which the inorganic salt is a potassium carbonate or potassium hydroxide.

26. The method according to claim 19, in which the inorganic salt is a potassium carbonate or potassium hydroxide.

27. The method according to claim 1, wherein the organic base is a triethylamine or pyridine.

28. The method according to claim 3, in which the organic salt compound of the formula (II) is a salt of triethylamine or pyridine.

29. The method according to claim 6, in which the organic base is a triethylamine or pyridine.

30. The method according to claim 1, wherein the compound of General formula (II) is reacted with an inorganic salt of the metal or the content of inorganic fillers in number, equal to at least 1 equivalent.

31. The method according to item 30, in which the compound of General formula (II) is reacted with an inorganic salt of the metal or organic base in a quantity equal to 2 equivalents.

32. The method according to claim 2, in which in the compound of General formula (II) R1represents CN; X represents CR4; each of R2and R4represents chlorine, R3represents trifluoromethyl; R5represents ethyl, n is 1.

33. The method according to claim 1, wherein in the compound of General formula (II) R1represents CN; X represents CR4; each of R2and R4represents chlorine, R3represents trifluoromethyl; R5represents ethyl, n is 1.

34. The method according to claim 1, including

a) the first stage is the interaction of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole with potassium carbonate with the formation of the potassium salt of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole;

b) the second stage, the interaction of the obtained potassium salt with methyl-stands with the formation of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(N-m-etilatsetatnyj)pyrazole.

35. The method according to claim 1, including

a) the first stage is the interaction of 1-(2,6-d is chloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)of pyrazole with triethylamine with the formation of the salt of triethylamine 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)pyrazole; and

b) the second stage is the interaction of the salts of triethylamine with iodine stands with the formation of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(N-methylethanolamine)pyrazole.

35. The method according to claim 2, including the interaction of the potassium salt of the compound 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)of pyrazole with methyl-stands with the formation of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(N-methylethanolamine)pyrazole.

37. The method according to claim 2, including the interaction of the salt of triethylamine compound 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifloromethyl-5-(ethoxyacetic)of pyrazole with iodine stands with the formation of 1-(2,6-dichloro-4-triptoreline)-3-cyano-4-trifluoromethyl-5-(N-methylacetamide) pyrazole.



 

Same patents:

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention elates to novel derivatives of uracil of the formula [I] possessing herbicide activity, a herbicide composition based on thereof and to a method for control of weeds. In derivatives of uracil of the formula [I] the group Q-R3 represents a substituted group taken among:

wherein a heterocyclic ring can be substituted with at least a substitute of a single species taken among the group involving halogen atom, (C1-C6)-alkyl-(C1-C6)-alkoxy; Y represents oxygen, sulfur atom, imino-group or (C1-C3)-alkylimino-group; R1 represents (C1-C3)-halogenalkyl; R2 represents (C1-C3)-alkyl; R3 represents OR7, SR8 or N(R9)R10; X1 represents halogen atom, cyano-group, thiocarbamoyl or nitro-group; X2 represents hydrogen or halogen atom wherein each among R7, R8 and R10 represents independently carboxy-(C1-C6)-alkyl and other substitutes given in the invention claim; R9 represents hydrogen atom or (C1-C6)-alkyl. Also, invention relates to intermediate compounds used in preparing uracil derivatives.

EFFECT: improved preparing method, valuable properties of compounds.

40 cl, 16 sch, 12 tbl, 65 ex

The invention relates to 1-methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiomethyl pyrazolylborate and herbicide tool based on them

The invention relates to new 1-aryl-5-(substituted)alkylidene the pyrazoles, methods for their preparation, to compositions containing these compounds, to methods of their use for combating arthropods, nematodes, helminths or protozoa pests

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention elates to novel derivatives of uracil of the formula [I] possessing herbicide activity, a herbicide composition based on thereof and to a method for control of weeds. In derivatives of uracil of the formula [I] the group Q-R3 represents a substituted group taken among:

wherein a heterocyclic ring can be substituted with at least a substitute of a single species taken among the group involving halogen atom, (C1-C6)-alkyl-(C1-C6)-alkoxy; Y represents oxygen, sulfur atom, imino-group or (C1-C3)-alkylimino-group; R1 represents (C1-C3)-halogenalkyl; R2 represents (C1-C3)-alkyl; R3 represents OR7, SR8 or N(R9)R10; X1 represents halogen atom, cyano-group, thiocarbamoyl or nitro-group; X2 represents hydrogen or halogen atom wherein each among R7, R8 and R10 represents independently carboxy-(C1-C6)-alkyl and other substitutes given in the invention claim; R9 represents hydrogen atom or (C1-C6)-alkyl. Also, invention relates to intermediate compounds used in preparing uracil derivatives.

EFFECT: improved preparing method, valuable properties of compounds.

40 cl, 16 sch, 12 tbl, 65 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to method for production of compounds of general formula I wherein R1 represents CN or CSNH2; X represents N or C each R2 and R4 are independently hydrogen or chlorine; R3 represents halogen, haloalkyl, haloalkoxy or SF3; R5 and R6 are independently alkyl; n = 0, 1 or 2. Claimed method includes reaction of compound of formula II , wherein substituents are as defined above; W represent hydrogen, with metal inorganic salt or organic amine to form salt of compound II as intermediate and further reaction of said salt with alkylating agent of formula III wherein R6 is as defined above; Y represents leaving group. In another embodiment compounds of formula I are obtained by reaction of metal inorganic salt or organic base of formula II with abovementioned alkylating agent of formula III.

EFFECT: essentially decreased formation of side products; target products of high purity.

37 cl, 4 ex

FIELD: organic chemistry, pesticides.

SUBSTANCE: invention relates to production of compounds of formula I

, wherein R1 represents CN or CSNH2; X represents N or CR4; R2 and R4 represent hydrogen or chlorine; and R3 represents halogen, haloalkyl, halooxy or SF5. Claimed method includes reaction of compound of formula II

with aqueous acid solution. Also disclosed are method for production of intermediate of formula II, method for production of compound of formula I including step of production of formula II followed by conversion thereof to target compound. Moreover disclosed are two intermediates for production of target products.

EFFECT: new pesticide compounds and method for production thereof.

13 cl, 2 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to 5-substituted alkylaminopyrazole derivatives of formula I , wherein R1 is CN; W is C-halogen; R1 is halogen; R3 is C1-C3-haloalkyl, C1-C3-haloalkoxy; R4 is hydrogen, C1-C6-alkenyl, C2-C6-alkynyl, C3-C7-cycloalkyl, COR8; A is C1-C12-alkylene; R5 is hydrogen, C3-C6-alkenyl, -(CH )qR7 or NR10R11; R5 is C1-C6-haloalkyl; as well as method for animal exogenous and endogenous pest controlling; pesticide composition and application of said compounds for production of veterinary drug. 5-Substituted alkylaminopyrazole derivatives are useful in pest controlling, including insects, arachnids and helminthes, such as nematodes.

EFFECT: new pesticide derivatives.

9 cl, 12 tbl, 20 ex

FIELD: organic chemistry.

SUBSTANCE: invention describes insecticide-acaricide substance used against extoparasites in dogs and cats. Substance represents derivative of phenylpyrazole of the formula (I) wherein in pyrazole structure cyano-group, trifluoromethylsulfenyl group and amino-group are bound at 3, 4 and 5 positions, respectively, and chlorine atoms are bound to phenyl cycle at 2 and 6 positions, and trichlorosilyl group is bound at 4 position. Substance protects dogs and cats against infection with fleas for 65 days after treatment and for 45 days after treatment of cats, and against infection with mites for 35 days, not less. In acute experiment toxicity of substance is characterized by value LD50 above 1300 mg/kg after its administration in stomach to dogs.

EFFECT: valuable properties of substance.

2 ex

FIELD: chemistry.

SUBSTANCE: described are derivatives of 5-substituted alkylaminopyrazoles of formula (I) , where R1 stands for CN, W stands for C-halogen; R2 stands for halogen, R3 stands for (C1-C3)-halogenoalkyl, R4 stands for (C1-C6)-alkyl, A stands for (C1-C12)-alkylene, R5 stands for (C1-C6)-alkyl, R6 stands for (C1-C6)-halogenoalkyl, n equals 2, or their pesticidely acceptable salts. Compounds demonstrate insecticidal activity and parasiticidal activity. The method of obtaining formula (I) is described, including interaction of compound of formula (II) with compound of formula (III) R5-O-A-NH2 and interaction on compound obtained with compound of formula (V) R4-L1.

EFFECT: obtaining derivatives which can be applied as pesticides.

3 cl, 6 tbl, 18 ex

FIELD: medicine.

SUBSTANCE: invention is related to antagonists of serotonin 5-HT6 receptors of common formula 1 and their pharmaceutically acceptable salts and/or hydrates, pharmaceutical compositions, dosage forms and methods of production. Invention also includes new compounds of formula 1.1. In formulae 1 and 1.1 , Ar represents aryl, selected from unnecessarily substituted phenyl or unnecessarily substituted 5-6-member heteroaryl, which contains atom of nitrogen or atom of sulfur and heteroatom; R1 represents atom of hydrogen, unnecessarily substituted C1-C5 alkyl; Ar represents aryl, selected from unnecessarily substituted phenyl or unnecessarily substituted 5-6-member heteroaryl, which contains atom of nitrogen or atom of sulfur as heteroatom; R1 represents atom of hydrogen, which is unnecessarily substituted C1-C5 alkyl; R21,R22, R31, R32 independently from each other represent atom of hydrogen or substituent of aminogroup, selected from unnecessarily substituted C1-C4 alkyl, unnecessarily substituted phenyl, or R31 and R32 together with atom of nitrogen, to which they are bound, create unnecessarily substituted saturated 6-member heterocycle, possibly containing atom of nitrogen in cycle; or R1 together with atom of nitrogen, to which it is bound, and R21 and R22 together with atom of nitrogen, to which they are bound, create substituted pyrimidine cycle. In formula 1.1 R4, R5 and R6 independently from each other represent atom of hydrogen, unnecessarily substituted C1-C3 alkyl or phenyl.

EFFECT: compounds of invention may find application for treatment and prevention of development of conditions and disorders of central nervous system.

13 cl, 11 dwg, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: invention proposes 5-member heterocyclic inhibitors of kinase p38, including kinase p38α and kinase p38β, based on pyrazoles and imidazoles, with the general formula given below , in which ring B is phenyl, and C is a pyrazole or imidazole ring, and the rest of the symbols assume values given in paragraph 1 of the formula of invention.

EFFECT: there are described pharmaceutical compositions containing said compounds, as well as methods of using the compounds and compositions, including a method of treating, preventing or suppressing one or more symptoms of diseases and conditions mediated by kinase p38 which include, but not limited to, inflammatory diseases and conditions.

31 cl, 6 tbl, 175 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of producing a compound (I), where X is N or CR4; R1 is CN or CSNH2; R2 and R4 are independently hydrogen or chlorine; and R3 is halogen, haloalkyl, haloalkoxy or SF5, n equals 0, 1 or 2. The method involves, at the first step, reaction of a compound of formula (IV), where X, R1, R2, R3, R4 and n assume values given above, with formaldehyde or a formaldehyde trimer or chemical equivalent thereof, to obtain an intermediate compound (V), where X, R1, R2, R3, R4 and n assume values given above; and at the second step, reaction of the compound of formula (V) with a reducing agent, preferably sodium borohydride. The invention also relates to an intermediate compound 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-hydroxymethylamino-4-trifluoromethyl thionyl pyrazole.

EFFECT: efficient method of obtaining the compounds.

3 cl, 1 ex

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