Method for production of pesticide agents

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

 

The present invention relates to a method for producing substituted pyrazole compounds.

The pyrazoles, such as compounds 5-amino-1-aryl-3-cyanopyridine, and their derivatives, such as fipronil, constitute an important class of insecticides. As described in the application WO 00/35884 and U.S. patent 5556873, some substituted compound 5-N-alkyl-N-alkoxyamino-1-aryl-3-cyanopyridine have valuable pesticidal properties.

The applicant developed a new method of synthesis for the preparation of intermediate compounds suitable for obtaining pesticide compounds substituted pyrazole.

Thus, the present invention relates to a method of obtaining compounds of General formula (I)

where

R1represents CN or CSNH2;

R2represents a hydrogen or chlorine; and

R3represents halogen or halogenated, or halogenoalkane, or SF5,

including the interaction of the compounds of formula (II)

where R1, R2and R3have the meanings indicated above; with a source of protons.

Source of protons used in this method according to the present invention preferably is an aqueous acid solution such as a solution of hydrogen chloride in water.

The reaction is carried out respectively in a suitable dissolve the e or in a solvent, which can partially be mixed or may not be mixed with water. Suitable solvents include hydrocarbon solvents such as toluene or xylene.

Number source of protons used in the reaction, respectively from 0.1 to 2 equivalents, preferably from 0.5 to 1.0 equivalent.

The reaction can be performed respectively at the temperature from minus 50 to 200°C, preferably from 50 to 100°C.

As for R1, R2and R3, R1is preferably CN; R2is preferably chlorine, and R3is preferably halogenated, mainly trifluoromethyl.

In accordance with the new method of synthesis is possible to obtain the compound (II); and another aspect of the present invention is a method of producing compound (II), as defined above, including the interaction of the compounds of General formula (III)

where R1, R2and R3have the meanings defined above; with a Quaternary ammonium salt.

The Quaternary ammonium salt may be of tetraalkylammonium halide, such as iodide or bromide, preferably of tetraalkylammonium bromide. Suitable bromide of tetraalkylammonium includes tetrabutylammonium bromide. The amount of salt of the halide used in the reactions is, respectively from 0.01 to 2 equivalents, preferably from 0.1 to 0.5 equivalents.

The reaction can be carried out in the presence of an organic solvent, which can partially be mixed or may not be mixed with water. Suitable solvents include hydrocarbon solvents such as toluene or xylene. The reaction is carried out respectively at a temperature of from 50 to 100°C.

The compound (III), above, can be obtained in accordance with the known method of synthesis, which involves the reaction of pyrazole compounds, known as fipronil, having the formula (IV)

with triethylorthoformate. This reaction can be carried out in the presence of an acid catalyst. Suitable catalyst includes paratoluenesulfonyl acid.

The compound (III) can also be treated Quaternary ammonium salt followed by treatment with an acid to obtain directly the compound (I) without isolation of compound (II).

The compound (I) can also be obtained by the interaction of fipronil (compound IV) with formaldehyde or a trimer of formaldehyde or its chemical equivalent, to obtain the intermediate compound (V)

where R1, R2, R3have the values specified above.

Then the intermediate connection is out (V) can interact with the regenerating agent to obtain the compound (I). Suitable reducing agent comprises sodium borohydride. Reducing agent may be present in an amount of from 1 to 5 equivalents.

Some of the compounds of formula (II), (III) and (V) are novel compounds and, in particular, another aspect of the present invention are new compounds:

3-cyano-1-(2,6-dichloro-4-triptoreline)-5-N-formyl-N-methylamino-4-triftormetilfullerenov (Compound II).

3-cyano-1-(2,6-dichloro-4-triptoreline)-5-ethoxymethyleneamino-4-triftormetilfullerenov (Compound III)

3-cyano-1-(2,6-dichloro-4-triptoreline)-5-hydroxymethylamino-4-triftormetilfullerenov (Compound V).

The compound (I)obtained by the method of the present invention, can be used as a starting material for the synthesis of another important pyrazole, which is known to possess pesticidal properties, and which corresponds to the General formula (VI).

where

R1represents CN or CSNH2;

X represents N or CR4;

each R2and R4independently represent hydrogen or chlorine;

R3represents halogen, halogenated, halogenoalkane or SF5;

each R5and R6independently represents alkyl group; and

n is 0, 1 or 2;

Obtaining the connection of the connection is based (I) is known from international patent application no WO 00/35884, which is included here as a reference. In particular, compound (I) reacts with ethoxyacetylene in the presence of triethylamine to obtain compound (VI).

Hereinafter the present invention will be illustrated in the following examples, not limiting the invention.

Example 1

Triethylorthoformate taken in large molar excess, interacts with fipronil (Compound IV) by boiling under reflux in the presence of 0.5 equivalents paratoluenesulfonyl acid to obtain 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-ethoxymethyleneamino-4-triftormetilfullerenov (Compound III).

Received the product immediately treated with 0.1 equivalent of tetrabutylammonium iodide in xylene at 100°C for 5 hours to obtain 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-(N-formyl-N-methylamino)-4-triftormetilfullerenov (Compound II). The intermediate product is immediately subjected to contact with an aqueous solution of hydrogen chloride to obtain 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-methylamino-4-triftormetilfullerenov in the quality of the final product (Compound I).

Example 2

5 equivalents of sodium methylate (30% solution in methanol) just added to the suspension 0,437 g of fipronil and 1.4 equivalents of paraformaldehyde in 3 ml of methanol to obtain 3-cyano-1(2,6-dichloro-4-triptoreline)-5-hydroxymethylamino-4-triftormetilfullerenov (Compound V) after 3 hours at 20° C and 1 hour at 60°C. Then to the intermediate product was added 1 equivalent of sodium borohydride to obtain the classical extraction and chromatographic separation of 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-methylamino-4-triftormetilfullerenov (Compound I).

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

where R1represents CN or CSNH2;

X represents N or CR4

R2and R4represent hydrogen or chlorine; R3represents halogen, or halogenated, or halogenoalkane, or SF5,

including the interaction of the compounds of formula (II)

where R1, X, R2and R3have the meanings defined above;

with the aqueous acid solution.

2. The method according to claim 1, in which R1is CN, R2is chlorine, and R3represents trifluoromethyl.

3. The method according to claim 1 or 2, in which the aqueous acid solution is a solution of hydrogen chloride in water.

4. The method according to any of the preceding paragraphs, carried out in the presence of a solvent.

5. The method according to claim 5, in which the solvent is toluene or xylene.

6. The method of obtaining the compound (II), as defined in claim 1, including the interaction of the compounds of the General formula (III)

where R1, X, R2and R3have the meanings given in claim 1;

with Quaternary ammonium salt.

7. The method according to claim 6, in which the Quaternary ammonium salt is a halide of tetraalkylammonium.

8. The method according to claim 6 or 7, in which the of tetraalkylammonium halide is bromide of tetraalkylammonium.

9. The method according to any of PP-8 carried out in the presence of an organic solvent.

10. The method according to claim 9, in which the solvent is toluene or xylene.

11. The method of obtaining the compound (I), as defined in claim 1, including the interaction of the compound (III), as defined in claim 6, with the Quaternary ammonium salt followed by the addition of acid.

12. The compound 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-N-formyl-N-methylamino-4-triftormetilfullerenov.

13. The compound 3-cyano-1-(2,6-dichloro-4-triptoreline)-5-ethoxymethyleneamino-4-triftormetilfullerenov.



 

Same patents:

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, 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.

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EFFECT: obtaining derivatives which can be applied as pesticides.

3 cl, 6 tbl, 18 ex

FIELD: medicine.

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13 cl, 11 dwg, 4 tbl, 11 ex

FIELD: chemistry.

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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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