CN103467380B - Substituted phenyl pyrazole amide derivative and preparation method and application thereof - Google Patents

Abstract

The present invention relates to a class of substituted phenylpyrazole amide derivatives with insecticidal activity represented by the general formula (I) and its preparation and application. On the basis of the existing pyrazole amide compounds, substituting nitro The benzene ring is introduced into the 1 position of the pyrazole ring, wherein R ¹ , R ² , A, Z, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are as defined in the specification. The technical effect of the present invention is: not only improving the drug resistance of the original compound, reducing the production cost, but also improving the insecticidal activity to some pests, especially very effective for Lepidoptera pests such as oriental armyworm, diamondback moth, etc. It is an insecticide with broad application prospects. (I).

Description

A class of substituted phenylpyrazole amide derivatives and its preparation method and application

technical field

The present invention relates to the synthesis technology of agricultural chemical insecticides, especially a class of substituted phenylpyrazole amide derivatives and their preparation methods and applications.

Background technique

Humans have been fighting agricultural pests since the history of farming. Effective control of agricultural pests is the key to increasing agricultural output, and it is also very important to forestry, animal husbandry, sideline, fishery and public health. The use of chemical pesticides is an effective means of pest control, but with the continuous expansion of the market, the resistance of pests, the service life of drugs and other issues and people's increasing attention to the environment, it is necessary to continuously develop high-efficiency, low-toxicity, environmental protection, Insecticide varieties with low cost and novel modes of action.

O-carboxamidobenzamides (ryanodine receptors) derivatives are effective insecticides developed to control Lepidoptera pests in recent years. DuPont of the United States, Bayer Agronomy and many domestic research institutions have applied for a large number of patents and reported a large number of compounds. See: WO2003016300, WO 2004067528, WO2007031213, WO 2008137970.

In order to design and synthesize new derivatives with insecticidal biological activity, improve insecticide resistance and reduce production costs, a class of substituted phenylpyrazole amide derivatives that have not been reported in the literature was designed and synthesized. The biological activity test showed that this derivatives have good insecticidal activity.

Contents of the invention

The object of the present invention is to provide a substituted phenylpyrazole amide derivative capable of improving the drug resistance of the original compound and increasing the insecticidal activity, its preparation method and application, based on the above technical analysis.

Technical scheme of the present invention:

A class of substituted phenylpyrazole amide derivatives has the following general formula (I):

I

In the formula:

Z is H, halogen, amino, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylamino or or ; Y is O, S or NH; A is or ;

U is H, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, halogenated C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or halogenated C ₃ -C ₆ cycloalkyl;

V is N or C; W is O, S or N;

R ¹ is H, halogen, nitro, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy;

R ² is H, halogen, cyano, nitro, C ₁ -C ₆ alkyl or halogenated C ₁ -C ₆ alkyl;

R ³ is C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, methylthio substituted alkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, halogenated C ₂ -C ₆ alkynyl, methylthio substituted unsaturated hydrocarbon group, C ₃ -C ₆ cycloalkyl or halogenated C ₃ -C ₆ cycloalkyl (excluding at least one C ₃ - C ₄ cycloalkyl substituted alkyl), substituted sulfonyl, substituted carbamoyl, substituted N-cyanosulfone (sulfur) imine or benzyl, wherein the H on the benzyl ring can be replaced by halogen, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl are further substituted;

R ⁴ is halogen, CF ₃ , CN, SOCF ₃ , SO ₂ CF ₃ , SOCHF ₂ , SO ₂ CHF ₂ , C ₁ -C ₆ alkoxy, halogenated C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, halogenated C ₁ -C ₆ alkylthio, C ₂ -C ₆ alkenyloxy, halogenated C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, halogenated C ₂ - C ₆ alkynyloxy, C ₂ -C ₆ alkanoyloxy or halogenated C ₂ -C ₆ alkanoyloxy;

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are H, halogen, NO ₂ , CN, NH ₂ , OH, C ₁ -C ₆ alkyl, halogenated C ₁ -C ₆ alkyl, C ₂ - C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, halogenated C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl or halogenated C ₃ -C ₆ ring Alkyl, C ₁ -C ₄ alkylsulfinyl, halogenated C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, halogenated C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylamino, C ₂ -C ₈ dialkylamino, C ₃ -C ₆ trialkylsilyl, C ₁ -C ₄ alkylthio or halogenated C ₁ -C ₄ alkylthio, At the same time, when A is NH, R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ cannot be H at the same time; R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ cannot be substituted by alkyl or haloalkyl. , when one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ is halogen or CH ₃ , at least one of the other substituents is non-halogen and non-CH ₃ ;

R ¹⁰ is amino, C ₁ -C ₆ alkyl, five-membered or six-membered heterocycle, phenyl or pyridyl, wherein the hydrogen on the five-membered or six-membered heterocycle, phenyl or pyridyl ring can be replaced by halogen, C ₁ -C ₆ alkyl or halogenated C ₁ -C ₆ alkyl is further substituted.

The halogen in the derivatives is fluorine, chlorine, bromine or iodine; the alkyl group is a straight chain or branched chain alkyl group; the haloalkyl group is a straight chain or branched chain alkyl group, and the hydrogen atoms on these alkyl groups can be part or all substituted by halogen atoms; "haloalkenyl", "haloalkynyl" and "halocycloalkyl" have the same definitions as the term "haloalkyl"; alkenyl is a straight chain or Branched chain with double bond at any position; alkynyl is straight chain or branched with 2-6 carbon atoms and triple bond at any position; heteroatom in five-membered or six-membered heterocycle is N, O or S.

The preparation method of a class of substituted phenylpyrazole amide derivatives, the synthetic route is as follows:

The preparation steps are as follows:

1) Mix the compound of general formula II, an organic solvent and water, add an oxidizing agent under stirring, then react for 0.5-48 hours at a temperature ranging from 0°C to the reflux temperature of the solvent, filter, remove the organic solvent under reduced pressure, and use an alkaline solution to After being purified to pH 12, the organic impurities were extracted with an organic solvent, and the aqueous phase was acidified to pH 1.5 to obtain the target compound III;

2) Dissolving the above-mentioned compound of general formula III in an organic solvent, adding oxalyl chloride and N,N-dimethylformamide (DMF), stirring and reacting at room temperature for 3-12 hours to prepare acid chloride IV;

3) When A is When the above acid chloride IV is dissolved in an organic solvent, it is then added dropwise to the organic solvent of the compound of the general formula VI to obtain a mixed solution, and a base is added to the mixed solution, and the reaction is carried out at a temperature of 0° C. to the solvent reflux temperature for 0.5-48 hours. Obtain the target compound I; when A is , dissolve potassium thiocyanate in an organic solvent, add phase transfer catalyst polyethylene glycol-400, stir and dissolve, react at room temperature for 0.5-4 hours, filter out the insoluble matter in the reaction solution to obtain a compound V solution, and add Acyl chloride IV is dissolved in an organic solvent, added dropwise to the compound V solution, and finally the resulting solution is mixed with the compound of general formula VI at a molar ratio of 1:1, and then reacted at a temperature of 0°C to the solvent reflux temperature for 2-12 hours to obtain Target compound of general formula I.

The organic solvent is dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, n-hexane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, N,N-di methylformamide or dimethylsulfoxide.

The oxidant is potassium permanganate, MCPBA, NaClO ₂ , NaIO ₄ /RuO ₂ , H ₂ O ₂ or ozone

The base is triethylamine, pyridine, 1,8-diaza-bicyclo(5,4,0)undec-7-ene, N,N-dimethylaniline, sodium hydroxide, potassium hydroxide , sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide.

The acid is methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, phosphoric acid ester, hydrochloric acid, sulfuric acid or phosphoric acid.

In the step 1), the mass ratio of the compound of the general formula II, the organic solvent and water is 1:2-50:2-50, and the molar ratio of the compound of the general formula II to the oxidizing agent is 1:3-11.

In the step 2), the molar ratio of the compound of the general formula III to oxalyl chloride is 1:1.5-4, and the molar ratio of the compound of the general formula III to N,N-dimethylformamide (DMF) is 1:0.05-0.15.

In the step 3), the mass ratio of acid chloride IV to organic solvent is 1:2-50, the mass ratio of VI compound to organic solvent is 1:2-50, and the molar ratio of acid chloride IV to the compound of general formula VI is 1:1 , the molar ratio of acid chloride IV to base is 1:1.5, the mass ratio of potassium thiocyanate to organic solvent is 1:10-80, the consumption of polyethylene glycol-400 is 0.5-1wt% of organic solvent, acid chloride and sulfur The molar ratio of potassium cyanate is 1:2.5.

The application of a class of substituted phenylpyrazole amide derivatives is used for the preparation of agricultural chemical insecticides, especially for the control of insects such as Oriental armyworm and diamondback moth; it can also be used as an active ingredient for agriculturally acceptable A pesticide composition composed of adjuvants is used for the control of insects.

The technical effect of the present invention is: the substituted phenylpyrazole amide derivative not only improves the drug resistance of the original compound, but also improves the insecticidal activity against certain pests; the preparation method is simple, easy to implement, and low in production cost; It is widely used in the preparation of agricultural chemical insecticides, especially for the control of insects such as Oriental armyworm and diamondback moth; it can also be used as an active ingredient in a pesticide composition composed of agriculturally acceptable adjuvants for the control of insects .

Detailed ways

The present invention is further described below in conjunction with embodiment, and its purpose is that content of the present invention can be better understood and embodies substantive characteristics of the present invention, so the example given should not be considered as limiting the protection scope of the present invention.

Example 1:

A preparation method of a substituted phenylpyrazole amide derivative, the substituted phenylpyrazole amide derivative is

3-Trifluoromethyl-1-(2-chloro-6-nitrophenyl) -N- [4-chloro-2-methyl-6-[(methyl)amino)-carbonyl]phenyl]- 1 H -pyrazole-5-carboxamide (derivative 01), the synthesis steps are as follows:

1) Preparation of 1,1,1-trifluoro-4-(furan-2-yl)-4-keto-2-en-2-ol sodium salt

Add 30 mL of absolute ethanol to a 100 mL single-necked round-bottom flask, add 1.15 g (50 mmol) of metallic sodium in 5 times under ice-cooling, stir until the sodium flakes disappear; remove the absolute ethanol under reduced pressure to obtain a white solid, add Add 50 mL of anhydrous diethyl ether to the reaction flask, then slowly add 7.10 g (50 mmol) ethyl trifluoroacetate dropwise under stirring, continue stirring for 5 min after the solid is completely dissolved; slowly add 5.5 g (50 mmol) 2-acetyl After the addition of furan, stir at room temperature for 8-12 hours; collect the white solid by suction filtration, wash with anhydrous ether to obtain 1,1,1-trifluoro-4-(furan-2-yl)-4-one-2 -en-2-ol sodium salt.

2) Preparation of 3-trifluoromethyl-5-furan-2-yl- 1H -pyrazole

In a 100 mL single-necked round bottom flask, 9.12 g (40 mmol) of 1,1,1-trifluoro-4-(furan-2-yl)-4-keto-2-en-2-ol sodium salt was dissolved in In the ethanol solution of 1 mol/L HCl, slowly add 4.11 g (60 mmol) of hydrazine hydrochloride, reflux reaction for 3-4 h, TLC detects that the reaction is complete; the reaction solution is cooled to room temperature, filtered, and the filtrate is decompressed After being dissolved, it was extracted with CH ₂ Cl ₂ , washed successively with saturated NaHCO ₃ solution and saturated brine, dried, and finally filtered to obtain 3-trifluoromethyl-5-furan-2-yl-1 H -pyridine azole.

3) Preparation of 3-trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-5-(furan-2-yl) -1H -pyrazole

In a 100 mL three-neck round bottom flask, 6.06 g (30 mmol) 3-trifluoromethyl-5 _- furan-2-yl- 1H -pyrazole, 6.22 g (45 mmol) _KCO were dissolved in Add 2 mL of water to 30 mL of DMF, raise the temperature to 50-60°C, and stir for 1 h; then slowly add a mixture of 6.91 g (36 mmol) 2,3-dichloronitrobenzene and 20 mL of DMF to the reaction solution, heated up to 125 °C for 3-4 h, and TLC detected that the reaction was complete; the reaction solution was desolvated under reduced pressure, extracted with ethyl acetate, successively with 1 mol L ^- 1 hydrochloric acid solution, saturated sodium bicarbonate solution, saturated Wash with brine, and finally desolvate under reduced pressure to obtain the crude product, which is directly carried out to the next reaction without purification.

4) Preparation of 3-trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid

In a 250 mL three-necked round-bottom flask equipped with a lye absorption device, the above 10.73 g (30 mmol) 3-trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-5 Dissolve the crude product of -(furan-2-yl)-1 H -pyrazole in 50 mL of acetonitrile, then add 20.41 g (150 mmol) of KH ₂ PO ₄ , 50 mL of water, and dropwise add 330 mmol of sodium chlorite below 0 ℃ (NaClO ₂ ) aqueous solution, the dropwise addition was completed, and the stirring reaction was continued for 4 h in an ice bath. TLC detected that the reaction was complete; filtered, the filtrate was decompressed to remove acetonitrile, and the concentration was 2 mol/L Potassium hydroxide solution was fully alkalized to pH 12. Then extract the organic impurities with ethyl acetate, acidify the aqueous phase with 2 mol/L hydrochloric acid solution to pH 1.5, precipitate a solid, filter it with suction, dry it, and finally separate it by column chromatography to obtain 3-trifluoromethyl-1- ((2-Chloro-6-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid.

5) Preparation of 2-amino-3-methyl-5-chlorobenzoic acid

Dissolve 9.98 g (66 mmol) of 2-amino-3-methylbenzoic acid in 50 mL of DMF, slowly add 8.81 g (66 mmol) of N-chlorosuccinimide (NCS), and heat to 100 ℃, reacted for 2 h, cooled and poured into 200 mL ice water, a white solid precipitated out, filtered, dissolved the solid with ethyl acetate, dried, precipitated to obtain a gray solid, washed with ether to obtain a white solid 2-amino-3- Methyl-5-chlorobenzoic acid.

6) Preparation of N -methyl-2-amino-3-methyl-5-chlorobenzamide

Dissolve 3.34 g (18 mmol) 2-amino-3-methyl-5-chlorobenzoic acid in 30 mL thionyl chloride, reflux for 4 h, remove thionyl chloride under reduced pressure, and dissolve the residue in 20 mL Tetrahydrofuran, in an ice-salt bath, slowly drop into 13.95 g (180 mmol) of tetrahydrofuran solution with a concentration of 40wt% methylamine aqueous solution, stir at room temperature for 8 h after dropping, remove tetrahydrofuran, dissolve in ethyl acetate, wash with water, organic The layer was dried and column chromatographed to obtain N -methyl-2-amino-3-methyl-5-chlorobenzamide after precipitation.

7) Preparation of 3-trifluoromethyl-1-(2-chloro-6-nitrophenyl) -N- [4-chloro-2-methyl-6-[((methyl)amino)-carbonyl] Phenyl] -1H -pyrazole-5-carboxamide

Dissolve 0.36 g (1.07 mmol) of 3-trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid in 20 mL of dichloromethane and add 0.20 g (1.6 mmol) oxalyl chloride and two drops of DMF, the mixture was reacted at room temperature for 3 h, and the solvent was removed under reduced pressure to obtain the crude acid chloride; the crude acid chloride was dissolved in 10 mL tetrahydrofuran and slowly dropped into 0.20 g (1.0 mmol) in a mixture of N -methyl-2-amino-3-methyl-5-chlorobenzamide and 0.16 g (1.6 mmol) triethylamine in 20 mL tetrahydrofuran, reflux for 4 h; Solvent, add 60 mL of dichloromethane to the reaction flask, then wash the organic layer with water and saturated saline solution, dry over anhydrous Na ₂ SO ₄ , precipitate under reduced pressure, and then obtain the target compound by vacuum column chromatography, light yellow Solid, mp 197-199°C.

Example 2:

A preparation method of a substituted phenylpyrazole amide derivative, the substituted phenyl pyrazole amide derivative is 3-trifluoromethyl-1-(2-chloro-4-nitrophenyl) -N- [ 4-Chloro-2-methyl-6-[((n-propyl)amino)-carbonyl]phenyl]-1 H -pyrazole-5-carboxamide (derivative 02), the synthesis steps are as follows:

1) Preparation of N -n-propyl-2-amino-3-methyl-5-chlorobenzamide

Dissolve 3.34 g (18 mmol) 2-amino-3-methyl-5-chlorobenzoic acid in 30 mL thionyl chloride, reflux for 4 h, remove thionyl chloride under reduced pressure, and dissolve the residue in 20 mL THF, in an ice-salt bath, slowly drop into a mixture of 10.64 g (180 mmol) n-propylamine and 20 mL THF, stir at room temperature for 8 h after dropping, remove THF, dissolve in ethyl acetate, wash with water, and dry the organic layer , Column chromatography after precipitation to obtain N -n-propyl-2-amino-3-methyl-5-chlorobenzamide.

2) Preparation of 3-trifluoromethyl-1-((2-chloro-4-nitro)phenyl)-5-(furan-2-yl) -1H -pyrazole

In a 100 mL three-necked round bottom flask, 6.06 g (30 mmol) of 3-trifluoromethyl-5-furan-2-yl- 1H -pyrazole, 6.22 g (45 mmol) _{of K2CO3} were dissolved in Add 2 mL of water to 30 mL of DMF, raise the temperature to 50-60 °C, and stir for 1 h; then slowly drop the mixture of 6.32 g (36 mmol) 3-chloro-4-fluoronitrobenzene and 20 mL of DMF into In the reaction solution, the temperature was raised to 125 °C for 3-4 h, and the reaction ^was complete as detected by TLC; Wash with saturated brine, and finally desolvate under reduced pressure to obtain the crude product, which is directly carried out to the next reaction without purification.

3) Preparation of 3-trifluoromethyl-1-((2-chloro-4-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid

In a 250 mL three-necked round-bottomed flask equipped with a lye absorption device, the above 10.73 g (30 mmol) 3-trifluoromethyl-1-((2-chloro-4-nitro)phenyl)-5 The crude -(furan-2-yl)-1H-pyrazole was dissolved in 50 mL of acetonitrile, then 20.41 g (150 mmol) of KH ₂ PO ₄ , 50 mL of water were added, and 330 mmol of sodium chlorite was added dropwise below 0 °C After the dropwise addition was completed, the reaction was continued to stir for 4 h in an ice bath. TLC detected that the reaction was complete; filtered, the filtrate was decompressed to remove acetonitrile, fully basified to pH 12 with a KOH solution with a concentration of 2 mol/L, and then washed with ethyl acetate The organic impurities were extracted with the ester, the aqueous phase was acidified to pH 1.5 with a hydrochloric acid solution with a concentration of 2 mol/L, the solid was precipitated, filtered with suction, dried, and finally separated by column chromatography to obtain 3-trifluoromethyl-1-((2-chloro -4-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid.

4) Preparation of 3-trifluoromethyl-1-(2-chloro-4-nitrophenyl) -N- [4-chloro-2-methyl-6-[((n-propyl)amino)-carbonyl ]phenyl] -1H -pyrazole-5-carboxamide

Dissolve 0.36 g (1.07 mmol) of 3-trifluoromethyl-1-((2-chloro-4-nitro)phenyl)-1 H -pyrazole-5-carboxylic acid in 20 mL of dichloromethane and add 0.20 g (1.6 mmol) of oxalyl chloride and two drops of DMF, the mixture was reacted at room temperature for 3 h, and the solvent was evaporated under reduced pressure to obtain the crude acid chloride; the obtained acid chloride was dissolved in 10 mL of tetrahydrofuran, and slowly dropped into 0.23 g (1.0 mmol) N -n-propyl-2-amino-3-methyl-5-chlorobenzamide and 0.16 g (1.6 mmol) triethylamine in 20 mL tetrahydrofuran solution, reflux for 4 h; The solvent was removed, and 60 mL of dichloromethane was added to the reaction flask, and then the organic layer was washed with water and saturated saline solution, dried over anhydrous Na ₂ SO ₄ , desolvated under reduced pressure, and then the target compound was obtained by vacuum column chromatography, Pale yellow solid, mp 210~212 ℃.

Example 3:

A preparation method of a substituted phenylpyrazole amide derivative, the substituted phenyl pyrazole amide derivative is 3-trifluoromethyl-1-((2,4-dinitro)phenyl) -N- [4-Chloro-2-methyl-6-[((methyl)amino)-carbonyl]phenyl]-1 H -pyrazole-5-carboxamide (derivative 03), the synthesis steps are as follows:

1) Preparation of 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-5-(furan-2-yl) -1H -pyrazole

In a 100 mL three-neck round bottom flask, dissolve 6.06 g (30 mmol) 3-trifluoromethyl-5-furan-2-yl- 1H -pyrazole, 2.52 g (45 mmol) KOH in 30 mL acetonitrile and 2 mL of water, then added 0.10 g (0.30 mmol) tetrabutylammonium bromide, stirred at room temperature for 1 h; then slowly added 7.29 g (36 mmol) of 2,4-nitrochlorobenzene in acetonitrile solution dropwise to the reaction solution , heated up to 50-60 °C for 3-4 h, and TLC detected that the reaction was complete; the reaction liquid was desolvated under reduced pressure, extracted with ethyl acetate, and successively used 1 mol L ^- 1 hydrochloric acid solution, saturated sodium bicarbonate solution, saturated Wash with brine, and finally desolvate under reduced pressure to obtain the crude product, which is directly carried out to the next reaction without purification.

2) Preparation of 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-1 H -pyrazole-5-carboxylic acid

In a 250 mL three-necked round-bottom flask equipped with a lye absorption device, the above 11.05 g (30 mmol) 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-5- The (furan-2-yl)-1 H -pyrazole crude product was dissolved in 50 mL of acetonitrile, and then 20.41 g (150 mmol) of KH ₂ PO ₄ and 50 mL of water were added, and 330 mmol of sodium chlorite was added dropwise below 0 °C Aqueous solution, after the dropwise addition, continue to stir and react for 4 h under ice bath, TLC detects that the reaction is complete; filter, remove acetonitrile from the filtrate under reduced pressure, fully alkalinize to pH 12 with 2 mol/L KOH solution, and then extract the organic Impurities, the aqueous phase was acidified to pH 1.5 with 2 mol/L hydrochloric acid solution, the solid was precipitated, filtered with suction, dried, and finally separated by column chromatography to obtain 3-trifluoromethyl-1-((2,4-dinitro)benzene base)-1 H -pyrazole-5-carboxylic acid.

3) Preparation of 3-trifluoromethyl-1-((2,4-dinitro)phenyl) -N- [4-chloro-2-methyl-6-[((methyl)amino)-carbonyl ]phenyl] -1H -pyrazole-5-carboxamide

Dissolve 0.37 g (1.07 mmol) of 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-1 H -pyrazole-5-carboxylic acid in 20 mL of dichloromethane and add 0.20 g (1.6 mmol) oxalyl chloride and two drops of DMF, and the mixture was reacted at room temperature for 3 h, and the solvent was evaporated under reduced pressure to obtain the crude acid chloride; g (1.0 mmol) N -methyl-2-amino-3-methyl-5-chlorobenzamide and 0.16 g (1.6 mmol) triethylamine in 20 mL tetrahydrofuran solution, reflux for 4 h; To remove the solvent, add 60 mL of dichloromethane to the reaction flask, then wash the organic layer with water and saturated saline solution, dry over anhydrous Na ₂ SO ₄ , desolvate under reduced pressure, and then obtain the target compound by vacuum column chromatography, light Yellow solid, mp 204~206 ℃.

The derivatives 01-488 prepared according to the preparation method of Examples 1-3 but using different raw materials are listed in Table 1 and Table 2, and some derivatives ¹ H NMR (Bruker AV400 spectrometer using tetramethylsilane as the internal standard ) data are included in Table 3

Table 1 1-1

1-2

1-3

1-4

1-5

1-6

1-7

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

Table 2

2-1

2-2

2-3

2-4

2-5

table 3

3-1

3-2

Example 4:

Use the derivatives (01-488) provided by the invention to test and verify the biological activity evaluation of pests:

Dissolve any derivative (01-488) provided by the present invention in solvent, water and surfactant, mix to form a homogeneous water phase, and dilute it with water to any desired concentration when used. The test objects and test methods are as follows:

1) Evaluation of the biological activity of Mythimna separata Walker: The tested insects are Mythimna separata Walker, a normal group raised indoors with corn leaves; the seedling corn leaves were dipped in the prepared solution by the leaf dipping method After drying, put it into a 7 cm diameter petri dish, insert the 4th instar larvae, and repeat each concentration 3 times; as a control, soak the corn leaves with acetone solution to raise the larvae, and observe the test results after 24 hours, 48 hours, and 72 hours.

2) Evaluation of the biological activity of Plutella xylostella: The tested insects were the 2nd instar larvae of Plutella xylostella ( Plutella xylostella (L.) ), which was a normal population raised normally in the room; using the leaf dipping method, the cabbage leaves were dipped in prepared leaves with tweezers. solution for 2-3 seconds, shake off the remaining liquid; 1 piece each time, 3 pieces in total for each sample; after the liquid medicine is dry, put it into a 10cm long straight test tube, and insert the 2nd instar diamondback moth larvae , cover the nozzle with gauze; place the test treatment in a standard treatment room, and observe the test results after 24 hours, 48 hours, and 72 hours.

The test results of the above tests are shown in Table 4 and Table 5.

Table 4

Mortality grades in the table: grade A is 100%-90%; grade B is 90%-70%; grade C is 70%-50%; grade D is 50%-0%.

Some compounds are more active than the reference drug Chlorantraniliprole, as shown in Table 5 below:

table 5

Claims (2)

1. a class substituted phenyl pyrazole amide derivatives, is characterized in that having following general formula (I):

（I）

In formula:

Z is y is NH; A is NH; R ¹for methyl; R ²for Cl; R ³for ethyl or sec.-propyl; R ⁴for CF ₃; R ⁷for nitro; R ⁹for Cl; R ⁵, R ⁶, R ⁸for H..

2. the application of class substituted phenyl pyrazole amide derivatives according to claim 1, is characterized in that: the pesticide composition being equipped with agriculture acceptable auxiliary agent composition as activeconstituents, for preventing and treating the purposes of insect.