KR970009725B1 - New pyrazolecarboxamides exhibiting insecticide and acaricide activity - Google Patents

Abstract

None.

Description

New parasolcarboxamides show insecticidal and tick removal effects

The present invention relates to compounds based on amides of 5-pyrazolecarboxylic acids.

More specifically, the present invention relates to a 5-pyrazolecarboxylic acid amide-based compound having a high insecticidal and mite removal effect, and a method for preparing the same and also for suppressing pest and mite damage in crops, everyday life, and livestock. It also relates to use in the back.

EP 289,879, 307,801, 329,020, 365,925, 405,808 and 462,573 disclose 5-pyrazolecarboxylic acid amide groups which show pesticidal and tick removal properties.

However, the pesticidal effect of the compounds of the European patents is limited. Attic giornate fitopatologiche (4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methylpyrazole-5-carboxamide in this regard is known as tebufenpyrad and corresponds to compound 51 of European Application No. 289,879. Basically, it shows limited insecticidality as a tick remover.

Applicants have found that by modifying benzyl groups bound to amide nitrogen atoms with appropriate halogenated substituents, they exhibit much greater pesticidal effects than known pyrazolecarboxyamides while maintaining high mite removal.

Accordingly, the present invention is based on the 5-pyrazolecarboxylic acid amide-based compound of formula (I).

Where R ₁ is a hydrogen atom, a straight or branched C ₁ -C ₄ alkyl or benzyl group,

R ₂ is a hydrogen atom or a straight or branched C ₁ -C ₄ alkyl group,

R _x represents a hydrogen atom, a chlorine atom such as fluorine or bromine, a straight or branched C ₁ -C ₄ alkyl or haloalkyl group, or R ₂ and R _x together represent an RHC- (CH ₂ ) _n -CH ₂ group Where R is a hydrogen atom C ₁ -C ₃ alkyl and n is an integer from 1 to 2,

R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a straight or branched C ₁ -C ₄ alkyl group,

X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom or a halogen atom such as chlorine fluorine or bromine,

-R _y is a straight or branched C ₃ -C ₆ haloalkoxyhaloalkoxy or haloalkoxyhaloalkoxythio group, a straight or branched C ₁ -C ₆ haloalkylthio group, a straight or branched C ₂ -C ₆ haloalkenyl group Or a straight or branched C ₃ -C ₆ haloalcohol haloalkenyl group.

Compounds of general formula (I) show high insecticidal and high mite removal effects.

Compounds of general formula (I) which are advantageous for these insecticidal and mite removal effects, for example,

The present invention also provides a process for preparing the compound of general formula (I).

Compounds of formula (I) can be obtained by reacting a 5-pyrazole-carboxylic acid derivative of formula (II) with benzylamine of formula (III).

Wherein R ₁ , R ₂ , and R _x are as defined above and Z is a halogen atom such as chlorine or bromine, a hydrogen group or a straight or branched C ₁ -C ₄ alkoxy group;

Where R ₃ , R ₄ , R ₅ , X ₁ , X ₂ , X ₃ , X ₄ and R _y have the same meanings as described above.)

The reaction is carried out with or without base and solvent.

When Z is chlorine or bromine atom, the reaction is carried out at a temperature from 0 ° C. to the boiling point of the reaction mixture (solvent + base and the two kinds of reactants) in the presence of an inorganic or organic base and an inert organic solvent. Examples of inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Examples of organic bases are pyridine and triethyleneamine. Examples of inert organic solvents include benzene, toluene, xylene, acetone, methyl ethyl ketone, chloroform, methylene chloride, ethyl acetate, ethyl ether, tetrahydrofuran, dioxane, acetonitrile, N, N-dimethylformamide, and N-methyl Pyrrolidone, dimethyl sulfoxide.

When Z is a hydroxyl group or an alkoxy group, the reaction is carried out in the absence of a base. In this case, it can also be carried out at a temperature of 150 ° C. to 250 ° C., with or without a high boiling solvent such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide.

5-pyrazolecarboxylic acid derivatives of general formula (III) are known (Bulletin dela Societe Chimie de France, 1966, page 293; Farmaco Ed. Sc., Vol. 22, 1967, page 692 and in Annalen der Chemie) , vol. 598, 1956, page 186) Benzylamine of formula (III) can also be prepared by known organic synthesis methods (Beilstein Handbuch der Organischen Chemie, vol. 12, chapter III, page 2343).

The compound of formula (I) according to the present invention exhibits great insecticidal and mite removal efficacy against insects and mites, insects, and eggs that cause harm in crops, livestock, and living environments.

In particular, the compounds of formula (I) include beetle (Leptinotarsa decemlineata, Callosobruch us chinensis etc), cicada (Macrosiphum euphorbiae, Myzus persicae, Psylla piri etc.), Aedes Aegypti, Musca domestica etc., and Spodotera littoralis, Chilo supressalis etc., Tetranychus urticae, Panonychus ulmi, Panonychus citri etc., Phytopus avellanae, Eriophyes vitis, Eriop hyes piri etc., and also tarsonemines p. ) Is effective. At the same time, the compounds of general formula (I) are low in toxicity to many worms, mammals, fish, amphibians and birds, and are not particularly toxic to plants. Because of their beneficial properties, they can be advantageously used in agriculture and horticultural crops, agricultural products and the environment, which frequently infest people with pests.

In practical use in agriculture and other fields, pesticide and tick remover compositions containing one or more compounds of formula (I) as active substances are frequently used.

The compositions can be used in the form of dry powders, wet powders, active concentrates, microemulsions, pastes, particles, solutions, suspensions and the like.

The choice of composition type depends on the particular application.

The composition is prepared according to a known method such as diluting the active substance with a solvent medium and a solid dilution in the presence of a surfactant. Suitable solid diluents or auxiliaries include kaolin, alumina, silica, talc, bentonite, gypsum, quartz, rhodiumite, aggolite, montmorillonite, diatomaceous earth, cellulose, starch and the like.

Suitable liquid inert diluents include water, including aromatic hydrocarbons (mixtures of xylol or alkylbenzoyl), aliphatic hydrocarbons (hexane, cyclohexane), chloroaromatics (chlorobenzene), alcohols (methinol, propanol, butanol, octanol), Esters (isobutyl acetate), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethyl amyl ketone), vegetable oils or inorganic oils, or mixtures thereof.

Suitable surfactants include wetting agents and anionic (polyethoxylated alkylphenols, polyethoxylated fatty alcohols), anionic (alkylbenzene sulfonates, alkylsulfonates) or cationic (tetravalent alkylammonium salts) emulsifiers. Include.

Dispersants (lignin and salts thereof, cellulose derivatives, alginates) and stabilizers (antioxidants, ultraviolet absorbers) can also be used.

To further extend the range of action of the composition, other pesticides may be added to other active ingredients such as mites, herbicides, fungicides, or sterilizers.

The concentration of the active ingredient in the composition can vary widely depending on the active compound and also depends on their application, environmental conditions and formulation form.

In general, the concentration of the active substance is 1 to 90%, in particular 10% to 40%.

The amount added depends on the type and extent of invasion, the type of composition used, climate and environmental factors. For practical farming, a compound dose of 50 g to 500 g per hectare is sufficient. The following examples are intended to illustrate the invention without being limited thereto.

Example 1

N- [3-Chloro-4- (2-trifluoromethoxy-1,1,2-trifluoro-ethoxybenzyl] -4-chloro-3-ethyl-1-methypyrazole-5-carboxide Preparation (Compound No. 1)

A mixture consisting of 2 ml of methylene chloride, 0.11 ml of triethylamine and 250 mg of 3-chloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) -benzylamine (0.77 mol) Add gradually to a solution of 166 mg (0.8 mmol) of 4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxylic acid softener in 3 ml methylene chloride. The resulting solution is stirred at room temperature for 5 hours. Then diluted with 10% hydrochloric acid solution, extracted with ethyl ether, and the organic phase is washed with saturated sodium bicarbonate solution and concentrated to dryness.

The obtained product was purified by silica gel chromatography eluting with hexane / ethyl acetate in an 8: 2 ratio. 250 mg of compound 1 are obtained at a melting point of 73-74 ° C.

¹ H-NMR (CDCl ³ ): δ at1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.5 (d, 2H); 5.9 (dt, 1 H); 7.0-7.5 (complex, 4H).

Example 2

Preparation of N- [3-Chloro-4- (2-trifluoromethoxy-1,1,2-trifluoro-ethoxybenzyl] -4-chloro-1,3-dimethylparazol-5-carboxamide (Compound No. 2)

3 ml of a mixture consisting of 2 ml of methylene chloride, 0.10 ml of trimethylamine and 250 mg of 3-chloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) -benzylamine (0.65 mole) Add gradually to a solution of 133 mg (0.69 mmol) of 4-chloro-1,3-dimethyl-5-pyrazolecarboxylic acid chloride in methylene chloride. The resulting solution is stirred at room temperature for 5 hours.

Then diluted with 105 hydrochloric acid solution, extracted with ethyl ether, and the organic phase is washed with saturated sodium bicarbonate solution and concentrated to dryness.

The obtained product was purified by silica gel chromatography eluting with hexane / ethyl acetate in an 8: 2 ratio. 200 mg of compound 2 is obtained at a melting point of 73-74 ° C.

¹ H-NMR (CDCl ₃ ): δ at 2.4 (s, 3H); 4.2 (s, 3 H); 4.6 (d, 2H); 6.0 (dt, 1 H); 7.0-7.7 (complex, 4H).

Example 3

Preparation of N- [4 (2-trifluoromethoxy-1,1,2-trifluoro-ethoxybenzyl] -4-chloro-3-ethyl-1-methpyrazole-5-carboxamide (Compound III number)

A mixture of 4 ml of methylene chloride, 0.22 ml of trimethylamine and 450 mg of 4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) -benzylamine (1.56 mole) was placed in 332 mg of 6 ml methylene chloride. (1.6 mmol) of 4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxylic acid chloride is gradually added to the dissolved solution. The resulting solution is stirred at room temperature for 4 hours.

Then diluted with 105 hydrochloric acid solution, extracted with ethyl ether, and the organic phase is washed with saturated sodium bicarbonate solution and then concentrated to dryness.

The obtained product was purified by silica gel chromatography eluting with hexane / ethyl acetate in an 8: 2 ratio.

490 mg of compound 3 is obtained at a 54 ° C. melting point.

¹ H-NMR (CDCl ₃ ): δ at1.2 (t, 3H); 2.55 (q, 2 H); 4.1 (s, 3 H); 4.5 (d, 2H); 5.9 (dt, 1 H); 6.8-7.4 (complex, 5H).

Example 4

The following compound was prepared by the method of Example 1-3.

N- [3,5-dichloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-3-ethyl-1-methpyrazole-5-car Radiation Mid (Compound No. 4): MP 67-68 ° C.

¹ H-NMR (CDCl ₃ ): δ at1.2 (t, 3H); 2.55 (q, 2 H); 4.1 (s, 3 H); 4.5 (d, 2H); 5.9 (dt, 1 H); 6.8-7.4 (complex, 5H).

N- [3,5-dichloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-1,3-ethyl-1-methipyrazole-5 Carboxamide (Compound No. 5): MP 84-85 ℃

¹ H-NMR (CDCl ₃ ): δ at 2.2 (s, 3H); 4 (s, 3H); 4.55 (d, 2 H); 6.1 (dt, 1 H); 7.15 (bt, 1 H); 7.35 (s, 2 H).

N- [4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy-benzyl] -4-chloro-3-ethyl-1-methypyrazole-5-carboxide (Compound No. 6 MP 72-73 ° C

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.56 (d, 2 H); 5.8 (dt, 1 H); 7.1 (bt, 1 H); 7.4 (d, 2 H); 7.65 (d, 2 H).

N- [4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-1,3-dimethypyrazole-5-carboxamide (Compound No. 7 ): MP 75-76 ℃

¹ H-NMR (CDCl ₃ ): δ at 2.2 (s, 3H); 4.1 (s, 3 H); 4.1 (s, 3 H); 4.65 (d, 2 H); 7.1 (bt, 1 H); 7.4 (d, 2 H); 7.65 (d, 2 H).

(Z) -N- [4- (2-chloro-3,3,2-trifluoroprop) -1-pinyl) benzyl] -4-chloro-3-ethyl-1-methylpyrazole-5-carbox Meade (Compound No. 8). M.P. 90-91 ℃

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.65 (d, 2 H); 7.1 (dt, 1 H); 7.25 (s, 1 H); 7.4 (s, 2 H); 7.75 (s, 2 H).

N- [2-chloro-4- (2-trifluoromethoxy-1,1,2-trifluoro-ethoxy) benzyl] -4-chloro-3-ethyl-1-methpyrazole-5-carbox Meade (Compound No. 9): MP 64-64 ℃

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.7 (d, 2 H); 5.9 (dt, 1 H); 7.1 (m, 1 H); 7.3 (bs, 2 H); 7.5 (d, 1 H).

N- [4- (2-peptafluoropropoxy-1,1,2-trifluoro-ethoxy) benzyl] -4-chloro-3-ethyl-1-methypyrazole-5-carboxamide No. 10): MP 80-81 ℃

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.6 (d, 2H); 6.15 (dt, 1 H); 7.1 (bt, 1 H); 7.2-7.5 (complex, 3H).

N- [4- (1,1,2,2-tetrafluorobrothylthio) benzyl] -4-chloro-3-ethyl-1-methpyrazole-5-carboxide (Compound No. 11): M.P. 85-86 ℃

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (q, 2H); 4.1 (s, 3 H); 4.65 (d, 2 H); 5.75 (tt, 1 H); 7.1 (bt, 1 H); 7.4 (d 2 H); 7.65 (d, 2 H).

N- [4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -2,6-demethyl-2,4,5,6-tetrahydroceclopentapyrazole- 3-carboxamide (Compound No. 12).

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.0 (m, 1 H); 2.6 (m, 3 H); 3.1 (m, 1 H); 4.2 (s, 3 H); 4.6 (d, 2H); 5.9 (dt, 1 H); 6.8-7.5 (complex, 5H).

N- [3-chloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -2,6-dimethyl-2,4,5,6-tetrahydrocyclopentapyra Sol-3-carboxamide (Compound No. 13).

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.6 (m, 1 H); 2.6 (s, 3 H); 3.1 (m, 1 H); 4.2 (s, 3 H); 4.6 (d, 2H); 6.0 (dt, 1 H); 7.1 (bt, 1 H); 7.2-7.5 (complex, 3H).

N- [3,5-dichloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -2,6-dimethyl-2,4,5,6-tetrahydrocyclo Pentapyrazole-3-carboxamide (Compound No. 14).

¹ H-NMR (CDCl ₃ ): δ at 1.2 (t, 3H); 2.0 (m, 1 H); 2.6 (m, 3 H); 3.1 (m, 1 H); 4.2 (s, 3 H); 4.6 (d, 2H); 6.1 (dt, 1 H); 7.2 (bt, 1 H); 7.35 (s, 2 H).

Example 5

Insecticidal and tick removal effects

a) Insecticidal effect on Leptinotarsa decemlineata larvae (L.D.)

Potatoes with 10 5-day-old Leptinotarsa decemlineata larvae are soaked in 10% by volume of acetone dispersion in the product (Compound 1-3). This dispersion also contains Tween 20 (0.05%). The mortality is measured after 48 hours and compared with potato crop larvae soaked in 10% acetone-water solution.

b) Tick elimination effect against tetranychus urticae adult (T.U.)

Tetranychus urticae A 10-percent acetone-water dispersion containing Tween 20 (0.05%) of the product compound (No. 1-3) is sprayed on a disc made from the soybean leaves of female adults.

The mortality rate is measured after 48 hours and is compared with the disc made in 10% acetone-water solution.

Table 1 shows the measurement results. The results are shown by the mortality of pests and ticks treated with compounds 1 to 3. Table 1 also shows comparative compounds corresponding to N- (4-tert-butylbenzyl) -4-chloro-3-ethyl-1-methylpyrazole-5-carboxamide (Compound No. 51 of European Application No. 289,879) The results for (RC) are also shown.

Claims (12)

5-pyrazolecarboxylic acid amide-based compound of formula (I) (Wherein R ₁ is a hydrogen atom, a straight or branched C ₁ -C ₄ alkyl group or a benzyl group, -R ₂ is a hydrogen atom, a straight or branched C ₁ -C ₄ alkyl group, -R _x is a hydrogen atom, a halogen atom such as chlorine, fluorine or bromine, a straight or branched C ₁ -C ₄ alkyl group or a haloalkyl group, or —R ₂ and R _x together represent an RHC— (CH ₂ ) n —CH ₂ group wherein R is a hydrogen atom or a C ₁ -C ₃ alkyl group and n is an integer from 1 to 2, R ₃ , R ₄ , and R ₅ are each invertively halogen atom, linear or branched C ₁ -C | ₄ alkyl group, -X ₃ , X ₄ , X ₅ and X ₄ are each independently a halogen atom such as chlorine, fluorine or bromine or a hydrogen atom, -R _y is a straight or branched C ₃ -C ₆ haloalkoxyhaloalkoxy or haloalkoxy haloalkylthio group, a straight or branched C ₁ -C ₆ haloalkylthio group, a straight or branched C ₂ -C ₆ haloalkenyl group, Or a straight or branched C ₃ -C ₆ haloalkoxyhaloalkenyl group.) Pesticides and tick removers composed of 5-pyrazolecarboxylic acid amide-based compounds of formula (I): (Wherein R ₁ is a hydrogen atom, a straight or branched C ₁ -C ₄ alkyl group or a benzyl group, -R ₂ is a hydrogen atom, a straight or branched C ₁ -C ₄ alkyl group, -R _x is a hydrogen atom, a halogen atom such as chlorine, fluorine or bromine, a straight or branched C ₁ -C ₄ alkyl group or a haloalkyl group, or —R ₂ and R _x together represent an RHC— (CH ₂ ) _n —CH ₂ group wherein R is a hydrogen atom or a C ₁ -C ₃ alkyl group and n is an integer from 1 to 2, -X ₁ , X ₂ , X ₃ and X ₄ are each independently a halogen atom such as chlorine, fluorine or bromine or a hydrogen atom, -R _y is a straight or branched C ₃ -C ₆ haloalkoxyhaloalkoxy or haloalkoxy haloalkylthio group, a straight or branched C ₁ -C ₆ haloalkylthio group, a straight or branched C ₂ -C ₆ haloalkenyl group, Or a straight or branched C ₃ -C ₆ haloalkoxyhaloalkenyl group.) 3. N- [3-chloro-4- (2-trifluoro-methoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-3-ethyl-1-methylpyra according to claim 2 Insecticide and a mite remover characterized by the above-mentioned sol-5-carboxamide. 3. N- [3-chloro-4- (2-trifluoro-methoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-1,3-dimethylpyrazole- according to claim 2 Insecticide or a mite remover characterized by 5-carboxamide. 3. N- [4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-3-ethyl-1-methyl-pyrazole-5- Insecticide or a tick removal agent characterized by consisting of carboxamide. The compound according to claim 2, wherein N- [3,5-dichloro-4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] 4-chloro-3-ethyl-1-methylpyra Insecticide and a mite remover characterized by sol-5-carboxamide. 3. N- [4- (2-trifluoromethoxy-1,1,2-trifluoroethoxy) benzyl] -4-chloro-3-ethyl-1-methyl-pyrazole-5- Insecticide or a tick removal agent characterized by consisting of carboxamide. A 5-pyrazole carboxylic acid derivative of the following general formula (III) is reacted with benzylamine of the following general formula (III). Where R ₁ , R ₂ and R _x are the meanings above and Z is a halogen element such as chlorine or bromine, a hydrogen group, or a straight or branched C ₁ -C ₄ alkylalkyl group Where R ₃ , R ₄ , R ₅ , X ₁ , X ₂ , X ₃ , X ₄ and R _y are as defined above) The process according to claim 8, wherein the reaction is carried out in the presence of an inorganic or organic base, also an inert solvent, and at a temperature from 0 ° C. up to the boiling point of the reaction mixture. The process according to claim 8, wherein the reaction is carried out in the presence of an inorganic or organic base, or an inert solvent, and at a temperature of from 150 ° C to 250 ° C. A composition showing the insecticidal and mite removal effect consisting of a solid auxiliary, liquid diluent or surfactant and a 5-pyrazolecarboxylic acid amide based compound of general formula (I). 12. The composition of claim 11, wherein the concentration of the 5-pyrazolecarboxylic acid amide base compound of formula (I) is from 1 to 90%.