WO2015051572A1

WO2015051572A1 - Class of substituted phenyl pyrazole amide derivatives and preparation method and use thereof

Info

Publication number: WO2015051572A1
Application number: PCT/CN2013/087579
Authority: WO
Inventors: 李正名; 张秀兰; 马金龙; 周莎; 熊丽霞; 李永强; 王宝雷
Original assignee: 南开大学; 李正名; 张秀兰; 马金龙; 周莎; 熊丽霞; 李永强; 王宝雷
Priority date: 2013-09-29
Filing date: 2013-11-21
Publication date: 2015-04-16
Also published as: CN103467380A; CN103467380B

Abstract

Disclosed are a class of substituted phenyl pyrazole amide derivatives as shown by general formula (I) and having an insecticidal activity, and a preparation method and the use thereof. On the basis of the existing pyrazole amide compounds, a benzene ring substituted with nitro or other groups is introduced at position 1 of a pyrazole ring, thus improving the pesticide resistance of the original compounds, lowering production costs and improving the insecticidal activity against certain pests, in particular being very effective against lepidopteran pests, such as oriental armyworm, Plutella xylostella, etc., and thus they are insecticides with a wide application prospect.

Description

Substituted phenylpyrazole amide derivative, preparation method and application thereof

The present invention relates to a synthetic technique for agrochemical insecticides, and more particularly to a class of substituted phenylpyrazole amide derivatives, and methods for their preparation and use.

Background technique

Since the history of mankind farming, it has continued to fight agricultural pests. Effective control of agricultural pests is key to increasing agricultural production and is also important for forestry, animal husbandry, deputy, fisheries and public health. The use of chemical pesticides is a means of effectively controlling pests. However, with the continuous expansion of the market and the resistance of pests, the service life of drugs and the increasing emphasis on the environment, it is necessary to continuously develop high-efficiency, low-toxicity, environmental protection, A new type of insecticide that is low cost and has a working mode.

O-carboxamide benzamides (Finedine receptors) derivatives are effective insecticides for the development and control of lepidopteran pests in recent years. DuPont, Bayer, and many domestic research institutes 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, and to improve insecticide resistance and reduce production cost, a class of substituted phenylpyrazole amide derivatives which have not been reported in the literature was designed and synthesized. The derivatives have better insecticidal activity.

Summary of the invention

The object of the present invention is to provide a substituted phenylpyrazole amide derivative capable of improving the resistance of an original compound and improving insecticidal activity, and a preparation method and application thereof, in view of the above technical analysis.

The technical solution of the invention:

A class of substituted phenylpyrazole amide organisms having the general formula (I):

In the formula:

o

Z is H, halogen, amino, cyano, dC ₆ alkyl, dC ₆ alkoxy, dC ₆ alkylamino or z Y Or ^vv R ¹⁰ ; Y is 0, S or H; A is

11 is 11, dC ₆ alkyl, halogenated dC ₆ alkyl, C ₂ -C ₆ alkenyl, halogenated C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, 3⁄4. ₂ -. ₆ alkynyl, C ₃ -C ₆ cycloalkyl or _3⁄4 generation. ₃ -. ₆ cycloalkyl;

V is N or C; W is 0, S or N;

RH, halogen, nitro, dC ₆ alkyl, halogenated dC ₆ alkyl or dC ₆ alkoxy;

1 ² is 11, halogen, cyano, nitro, dC ₆ alkyl or halogenated dC ₆ alkyl;

R ³ is dC ₆ alkyl, ^ dC ₆ alkyl, methylthio substituted alkyl, C ₂ -C ₆ alkenyl, ^ C ₂ -C ₆ alkyl, C ₂ -C ₆ alkynyl, 3⁄4 . ₂ -. ₆ alkynyl, methylthio substituted unsaturated hydrocarbon, C ₃ -C ₆ cycloalkyl or halogenated C ₃ -C ₆ cycloalkyl (excluding alkyl substituted by at least one C ₃ -C ₄ cycloalkyl) a substituted sulfonyl group, a substituted carbamoyl group, a substituted N-cyanosulfone (thio)imide or a benzyl group, wherein H on the benzyl ring may be further substituted by halogen, dC ₆ alkyl, halogenated dC ₆ alkyl;

R ⁴ is halogen, CF ₃ , CN, SOCF ₃ , S0 ₂ CF ₃ , SOCHF ₂ , S0 ₂ CHF ₂ , dC ₆ alkoxy, halogenated dC ₆ alkoxy, dC ₆ alkylthio, halogenated dC ₆ Alkylthio, C ₂ -C ₆ alkenyloxy, halo C ₂ -C ₆ -oxyl, C ₂ -C ₆ alkynyloxy, 3⁄4. ₂ -. ₆ alkynyloxy, C ₂ -C ₆ alkanoyloxy or C ₂ -C ₆ substituting ^ alkanoyloxy;

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are H, halogen, N0 ₂ , CN, H ₂ , OH, dC ₆ alkyl, halogenated dC ₆ alkyl, C ₂ -C ₆ alkenyl, 3⁄4 generation. ₂ -. ₆ alkenyl, C ₂ -C ₆ alkynyl, 3⁄4 generation. ₂ -. ₆ alkynyl, C ₃ -C ₆ cycloalkyl or halo c ₃ -c ₆ cycloalkyl, dC ₄ alkylsulfinyl, halo dC ₄ alkylsulfinyl, dC ₄ alkylsulfonyl, halogen DC ₄ alkylsulfonyl, dC ₄ alkylamino, C ₂ -C ₈ dialkylamino, C ₃ -C ₆ trialkylsilyl, dC ₄ alkylthio or halogenated dC ₄ alkylthio, Meanwhile, when A is NH, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ cannot be H at the same time; R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ cannot be substituted by only one alkyl group or halogenated alkyl group. 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 ^1Q is an amino group, a dC ₆ alkyl group, a five- or six-membered heterocyclic ring, a phenyl group or a pyridyl group, wherein a hydrogen on a five- or six-membered heterocyclic ring, a phenyl or pyridyl ring may be halogen, dC ₆ alkyl Or a halogenated dC ₆ alkyl group is further substituted.

The halogen in the derivative is fluorine, chlorine, bromine or iodine; the alkyl group is a linear or branched alkyl group; a straight or branched alkyl group, the hydrogen atom on these alkyl groups may be partially or completely substituted by a halogen atom; the definitions of "haloalkenyl", "haloalkynyl" and "halocycloalkyl" The term "haloalkyl" is the same; alkenyl is straight or branched with 2 to 6 carbon atoms and may have a double bond at any position; alkynyl is a straight or branched chain having 2 to 6 carbon atoms There may be a triple bond at any position; the hetero atom in the five- or six-membered heterocyclic ring is N, 0 or S.

The preparation steps are as follows:

1) Mixing the compound of the general formula II, an organic solvent and water, adding an oxidizing agent under stirring, and then reacting at a temperature of 0 to a reflux temperature of the solvent for 0.5 to 48 hours, after filtering, removing the organic solvent under reduced pressure, and alkalizing with an alkali solution. After the pH 12, the organic impurities are extracted with an organic solvent, and the aqueous phase is acidified to pH 1.5 to obtain the target compound III;

2) The above compound of the general formula III is dissolved in an organic solvent, oxalyl chloride and hydrazine, hydrazine-dimethylformamide (DMF) are added, and the reaction is stirred at room temperature for 3-12 hours to obtain an acid chloride IV;

U

3) When ^hydrazine is ^hydrazine , the above acid chloride IV is dissolved in an organic solvent, and then added dropwise to an organic solvent of the compound of the formula VI to obtain a mixed solution, and a base is added to the mixture at a temperature of 0! Solvent reflux temperature

U

^ ^丫ΝΗ

The reaction is carried out for 0.5-48 hours to obtain the target compound I; when the hydrazine is S, the potassium thiocyanate is dissolved in an organic solvent, and the phase transfer catalyst polyethylene glycol-400 is added, stirred and dissolved, and reacted at room temperature for 0.5-4 hours. , insoluble matter in the reaction solution is filtered off to obtain a solution of the compound V, and the acid chloride IV is dissolved in an organic solvent, added dropwise to the solution of the compound V, and finally, the obtained solution is mixed with the compound of the formula VI by a molar ratio of 1:1 at a temperature. It is 0 °. The reaction is carried out at a reflux temperature of the solvent for 2 to 12 hours to obtain a compound of the formula I. The organic solvent is dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane, n-hexane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, hydrazine, hydrazine-di Methylformamide or dimethyl sulfoxide.

The oxidizing agent is potassium permanganate, MCPBA, NaC10 ₂ , NaI0 ₄ /Ru0 ₂ H ₂ 0 ₂ or ozone. The base is triethylamine, pyridine, 1,8-diaza-bicyclic (5,4,0 11-carbon-7-ene, hydrazine, hydrazine-dimethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium t-butoxide or potassium t-butoxide.

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

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

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

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

The use of a class of said substituted phenylpyrazole amide derivatives for the preparation of agrochemical insecticides, especially for the control of insects such as oriental armyworms and diamondback moths; The pesticide composition composed of the auxiliary agent is used for controlling insects.

The technical effect of the invention is that the substituted phenylpyrazole amide derivative not only improves the resistance of the original compound, but also improves the insecticidal activity against certain pests; the preparation method is simple, easy to implement, and the production cost is low; It is widely used in the preparation of agrochemical insecticides, especially for the control of insects such as Oriental armyworm and Plutella xylostella; it can also be used as an active ingredient to distribute agriculturally acceptable adjuvants for the control of insects. .

detailed description

The invention is further described in the following examples, which are intended to provide a better understanding of the nature of the invention.

Example 1

A process for the preparation of a substituted phenylpyrazole amide derivative which is 3-trifluoromethyl-1-(2-chloro-6-nitrophenyl)-N-[ 4-chloro-2-methyl-6-[(methyl)amino)-carbonyl]phenyl]-1H- Pyrazole-5-carboxamide (derivative 01), the synthesis steps are as follows:

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

Add 30 mL of absolute ethanol to a 100 mL single-neck round bottom flask, add 1.15 g (50 mmol) of sodium metal in 5 portions in an ice bath, stir the reaction until the sodium tablets disappear; remove the anhydrous ethanol under reduced pressure to obtain a white solid. 50 mL of anhydrous ether was added to the reaction flask, and then 7.10 g (50 mmol) of ethyl trifluoroacetate was slowly added dropwise with stirring until the solid was completely dissolved and stirring was continued for 5 min; 5.5 g (50 mmol) of 2-acetyl was slowly added dropwise. The furan was stirred at room temperature for 8-12 hours; the white solid was collected by suction and washed with anhydrous diethyl ether to give 1,1,1-trifluoro-4-(furan-2-yl;)-4-one- Sodium 2-en-2-ol.

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

9.12 g (40 mmol) of 1,1,1-trifluoro-4-(furan-2-yl)-4-one-2-en-2-ol sodium salt was dissolved in a 100 mL one-neck round bottom flask In a 1 mol/L HCl solution of ethanol, 4.11 g (60 mmol) of hydrazine hydrochloride was slowly added, and the reaction was refluxed for 3-4 h. The reaction was completed by TLC. The reaction mixture was cooled to room temperature, filtered, and the filtrate was evaporated. After the solution, it is extracted with CH ₂ C1 ₂ , washed with saturated NaHC0 ₃ solution, saturated brine, dried, and finally filtered and then evaporated to give 3-trifluoromethyl-5-furan-2-yl-1H-pyrazole. .

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

In a 100 mL 3-neck round bottom flask, 6.06 g (30 mmol) of 3-trifluoromethyl-5-furan-2-yl-1H-pyrazole, 6.22 g (45 mmol) of K ₂ C0 _{3 was} dissolved in 30 In mL DMF, dilute 2 mL of water, warm to 50-60 °C, stir the reaction for 1 h; then slowly add a mixture of 6.91 g (36 mmol) of 2,3-dichloronitrobenzene and 20 mL of DMF. In the reaction solution, the temperature is raised to 125 ° C for 3-4 h, and the reaction is completed by TLC; the reaction solution is decomposed under reduced pressure, and extracted with ethyl acetate. 1 ηηοΐ·!/ ¹ hydrochloric acid solution, saturated sodium bicarbonate solution The mixture was washed with saturated brine, and finally, the crude product was obtained by desolvation under reduced pressure, and the next reaction was carried out without purification.

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

In a 250 mL 3-neck round bottom flask equipped with an lysate, the above 10.73 g (30 mmol - trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-5- ( The crude furan-2-yl)-1H-pyrazole was dissolved in 50 mL of acetonitrile, then 20.41 g (150 mmol) KH ₂ P0 ₄ , 50 mL of water was added, and 330 mmol of sodium chlorite (NaC10) was added dropwise below 0 °C. ₂ ) The aqueous solution was stirred for 4 h after the completion of the ice bath, and the reaction was completed by TLC. After filtration, the filtrate was decompressed to remove acetonitrile, and alkalized to pH 12 with a concentration of 2 mol/L potassium hydroxide solution. Then, the organic impurities were extracted with ethyl acetate, and the aqueous phase was acidified to pH 1.5 with a hydrochloric acid solution of 2 mol/L, and the solid was precipitated, suction filtered, dried, and finally chromatographed to give 3-trifluoromethyl-1-(( 2-chloro-6-nitro)phenyl)-1H- Pyrazole-5-carboxylic acid.

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

9.98 g (66 mmol) of 2-amino-3-methylbenzoic acid was dissolved in 50 mL of DMF, and 8.81 g (66 mmol) of N-chlorosuccinimide (NCS) was slowly added thereto, and then heated to 100. V, reaction for 2 h, cooled, poured into 200 mL of ice water, a white solid precipitated, filtered, solid was dissolved in ethyl acetate, dried and evaporated to give an off-white solid. Methyl-5-chlorobenzoic acid.

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

Dissolve 3.34 g (18 mmol) of 2-amino-3-methyl-5-chlorobenzoic acid in 30 mL of thionyl chloride, reflux for 4 h, remove thionyl chloride under reduced pressure, and dissolve the residue in 20 mL Tetrahydrofuran, ice-cold bath, slowly drip into 13.95 g (180 mmol) 40% by weight aqueous solution of methylamine in tetrahydrofuran solution, drip at room temperature for 8 h, remove tetrahydrofuran, ethyl acetate dissolved, washed, organic The layer was dried and subjected to column chromatography to give N-methyl-2-amino-3-methyl-5-chlorobenzamide.

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

0.36 g (1.07 mmol) of 3-trifluoromethyl-1-((2-chloro-6-nitro)phenyl)-1H-pyrazole-5-carboxylic acid, dissolved in 20 mL of dichloromethane, added 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 evaporated under reduced pressure to give crude acid chloride. The crude acid chloride was dissolved in 10 mL of tetrahydrofuran and slowly dropped to 0.20 g (1.0 mmol) a mixture of N-methyl-2-amino-3-methyl-5-chlorobenzamide and 0.16 g (1.6 mmol) of triethylamine in 20 mL of tetrahydrofuran, refluxing for 4 h; 60 mL of methylene chloride was added to the reaction flask, and the organic layer was washed with water and a saturated aqueous sodium chloride solution, dried over anhydrous Na ₂ SO ₄ , and evaporated to dryness. , mp 197-199 °C.

Example 2:

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

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

3.34 g (18 mmol) of 2-amino-3-methyl-5-chlorobenzoic acid was dissolved in 30 mL of thionyl chloride, refluxed 4 h, the thionyl chloride was removed under reduced pressure, the residue was dissolved in 20 mL of tetrahydrofuran, and the mixture was poured into a mixture of 10.64 g (180 mmol) of n-propylamine and 20 mL of tetrahydrofuran. After stirring for 8 h, the tetrahydrofuran was removed, the ethyl acetate was dissolved, washed with water, and the organic layer was dried, and then evaporated to give 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 3-neck round bottom flask, 6.06 g (30 mmol) of 3-trifluoromethyl-5-furan-2-yl-1H-pyrazole, 6.22 g (45 mmol) of K ₂ C0 _{3 was} dissolved in 30 In mL DMF, add 2 mL water, warm to 50-60 °C, stir the reaction for 1 h; then slowly add a mixture of 6.32 g (36 mmol) 3-chloro-4-fluoronitrobenzene and 20 mL DMF. In the reaction solution, the temperature is raised to 125 ° C for 3-4 h, and the reaction is completed by TLC; the reaction solution is decomposed under reduced pressure, and extracted with ethyl acetate. 1 ηηοΐ·!/ ¹ hydrochloric acid solution, saturated sodium bicarbonate solution The mixture was washed with saturated brine, and finally, the crude product was obtained by desolvation under reduced pressure, and the next reaction was carried out without purification.

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

In a 250 mL three-necked round bottom flask equipped with an alkali absorption apparatus, the above 10.73 g (30 mmol - 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 P0 ₄ , 50 mL of water was added, and 330 mL of sodium chlorite solution was added dropwise at 0 ° C. After the completion of the dropwise addition, the reaction was stirred for 4 h, and the reaction was completed by TLC. After filtration, the filtrate was evaporated under reduced pressure to acetonitrile, and then fully alkalized to pH 12 with a 2 mol/L KOH solution, and then ethyl acetate. The organic impurities were extracted, and the aqueous phase was acidified to pH 1.5 with a hydrochloric acid solution having a concentration of 2 mol/L, and the solid was precipitated, suction filtered, dried, and finally subjected to column chromatography to obtain 3-trifluoromethyl-1-((2-chloro-) 4-Nitro)phenyl)-1H-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]pyrazole-5-carboxamide

0.36 g (1.07!!^!^-trifluoromethyl-^^chloro-nitro; phenylpyrazole-carboxylic acid, dissolved in 20 mL of dichloromethane, added 0.20 g (1.6 mmol) of oxalyl chloride and two DMF was added dropwise, and the mixture was reacted at room temperature for 3 h. The solvent was evaporated under reduced pressure to give crude acid chloride. The obtained acid chloride was dissolved in 10 mL of tetrahydrofuran, and 0.23 g (1.0 mmol) N-n-propyl group was slowly added dropwise in an ice bath. 2-Amino-3-methyl-5-chlorobenzamide was reacted with 0.16 g (1.6 mmol) of triethylamine in 20 mL of tetrahydrofuran for 4 h. The solvent was removed under reduced pressure and 60 was added to the reaction flask. After methylene chloride, the organic layer was washed with water and a saturated aqueous solution of sodium chloride, dried over anhydrous Na ₂ SO ₄ , and evaporated to dryness. Color solid, mp 210-212 °C.

Example 3:

A process for the preparation of a substituted phenylpyrazole amide derivative which is 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-N- [4-Chloro-2-methyl-6-[((methyl)amino)-carbonyl]phenyl; //-pyrazole-5-carboxamide (derivative 03), the synthesis procedure is as follows:

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

In a 100 mL 3-neck round bottom flask, 6.06 g (30 mmol) 3-trifluoromethyl-5-furan-2-yl-1H-pyrazole, 2.52 g (45 mmol) KOH was dissolved in 30 mL acetonitrile In a solution of 2 mL water, 0.10 g (0.30 mmol) of tetrabutylammonium bromide was added, and the reaction was stirred at room temperature for 1 h; then 7.29 g (36 mmol) of 2,4-nitrochlorobenzene in acetonitrile was slowly added dropwise to the reaction. In the liquid, the temperature is raised to 50-60 °C for 3-4 h, and the reaction is complete by TLC; the reaction solution is decomposed under reduced pressure, and extracted with ethyl acetate. The solution of hydrochloric acid with 1 ηηοΐ·!/ ¹ , saturated sodium bicarbonate The solution was washed with saturated brine, and finally the mixture was evaporated to dryness to give a crude product.

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

The above 11.05 g (30 mmol - trifluoromethyl-1-((2,4-dinitro)phenyl)-5-(furan) was placed in a 250 mL 3-neck round bottom flask equipped with an lysing apparatus. -2-yl)-1H-pyrazole was dissolved in 50 mL of acetonitrile, then 20.41 g (150 mmol) of KH ₂ P0 ₄ , 50 mL of water was added, and 330 mL of sodium chlorite solution was added dropwise at 0 ° C. After the dropwise addition, the reaction was stirred for 4 h, and the reaction was completed by TLC. After filtration, the filtrate was evaporated under reduced pressure to acetonitrile, and then fully basified to pH 12 with 2 mol/L KOH solution, and then organic impurities were extracted with ethyl acetate. The aqueous phase was acidified to pH 1.5 with a 2 mol/L hydrochloric acid solution, and the solid was precipitated, suction filtered, dried, and finally purified by column chromatography to give 3-trifluoromethyl-1-((2,4-dinitro)phenyl) -1H-pyrazole-5-carboxylic acid.

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

0.37 g (1.07 mmol) of 3-trifluoromethyl-1-((2,4-dinitro)phenyl)-1H-pyrazole-5-carboxylic acid, dissolved in 20 mL of dichloromethane, added 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 evaporated under reduced pressure to give crude acid chloride. The crude acid chloride was dissolved in 10 mL of tetrahydrofuran, and slowly dropped into 0.20 g in an ice bath. (1.0 mmol) N-methyl-2-amino-3-methyl-5-chlorobenzamide and 0.16 g (1.6 mmol) of triethylamine in 20 mL of tetrahydrofuran, refluxing for 4 h; Solvent, add 60 mL of dichloromethane to the reaction flask, and then wash with water and saturated saline solution respectively. The organic layer was dried over anhydrous N S0 _4, solvent evaporation under reduced pressure, then vacuum column chromatography to give the title compound as a pale yellow solid, mp 204-206 ° C.

The derivatives 01-488 prepared according to the preparation methods of Examples 1-3 but using different raw materials are listed in Table 1, Table 2, and the partial derivatives 1H MR (Bruker AV400 spectrometer using tetramethylsilane as the internal standard). Data are listed in Table 3

Table 1 1-1

1-2

1-3

1-4

^{o. AY 1 2 3 4 5} 6 7 8 9 m.p. RC)

95 A ₂ NH CH ₃ CI cyclopropyl CF ₃ HH CN H CI -

96 A ₂ NH CH ₃ CI t-C4 CF ₃ HH CN H CI -

97 Ai NH H CI CH ₃ CF ₃ N0 ₂ HHH CI -

98 Ai NH H CI nC ₃ H ₇ CF ₃ N0 ₂ HHH CI -

99 Ai NH H CI iC ₃ H ₇ CF ₃ N0 ₂ HHH CI -

100 A _l NH H CI t-C4H9 CF ₃ N0 ₂ HHH CI -

101 A _l NH H CI cyclopropyl CF ₃ N0 ₂ HHH CI -

102 A _l NH H CI CH ₃ CF ₃ HH N0 ₂ H CI -

103 A _l NH H CI nC ₃ H ₇ CF ₃ HH N0 ₂ H CI -

104 A _l NH H CI iC ₃ H ₇ CF ₃ HH N0 ₂ H CI -

105 A _l NH H CI t-C4H9 CF ₃ HH N0 ₂ H CI -

106 A _l NH H CI cyclopropyl CF ₃ HH N0 ₂ H CI -

107 A ₂ NH H CI CH ₃ CF ₃ N0 ₂ HHH CI -

108 A ₂ NH H CI nC ₃ H ₇ CF ₃ N0 ₂ HHH CI -

109 A ₂ NH H CI iC ₃ H ₇ CF ₃ N0 ₂ HHH CI -

110 A ₂ NH H CI t-C4H9 CF ₃ N0 ₂ HHH CI -

111 A ₂ NH H CI cyclopropyl CF ₃ N0 ₂ HHH CI -

112 A _l NH H CI CH ₃ CF ₃ CN HHH CI -

_{_{113 A l NH H CI nC 3}} H 7 CF 3 CN HHH CI -

114 A _l NH H CI iC ₃ H ₇ CF ₃ CN HHH CI -

115 A _l NH H CI t-C4H9 CF ₃ CN HHH CI -

116 A _l NH H CI cyclopropyl CF ₃ CN HHH CI -

117 A _l NH H CI CH ₃ CF ₃ HH CN H CI -

118 A _l NH H CI nC ₃ H ₇ CF ₃ HH CN H CI -

119 A _l NH H CI iC ₃ H ₇ CF ₃ HH CN H CI -

120 A _l NH H CI t-C4 CF ₃ HH CN H CI - 1-6

1-

1-8

1-9

1-10

1-11

1-12

1-13

1-14

1-15

1-16

Table 2

2-1

No. AZ ^{1 2 4 5 6 7 8 9} melting point rc)

397 A _l H CH ₃ CI CF ₃ N0 ₂ HHH CI -

398 A _l H CH ₃ CI CF ₃ HH N0 ₂ H CI -

399 A _l H CH ₃ CI CF ₃ N0 ₂ H N0 ₂ HH - 2-2

2-3

2-4

2-

table 3

3-1

3-2

Example 4:

Using the derivatives (01 to 488) provided by the present invention to test and verify the biological activity evaluation of the pests: Dissolving any of the derivatives (01 to 488) provided by the present invention in a solvent, water and a surfactant, and mixing It is synthesized into a uniform aqueous phase. It can be diluted with water to any desired concentration. The test objects and test methods are as follows:

1) Evaluation of the biological activity of oriental armyworm: The test insect is the oriental armyworm (ythimr s ara ta Walker), the normal population raised indoors with corn leaves; using the leaf-leaching method, the impregnated seedling corn leaves have been configured In the solution; dry and put into a 7 cm diameter culture dish, access 4th instar larvae, repeat each concentration 3 times; control the larvae with corn leaf impregnated with acetone solution, observe the test after 24 hours, 48 hours, 72 hours result.

2) Evaluation of the biological activity of Plutella xylostella: The test insect is Plutella xylostella 2nd infancy !k CP!ute!ki xyhste!ki

(L.) ) , is the normal group normally raised indoors; using the dip leaf method, dip the cabbage leaves with the tweezers in the prepared solution for 2-3 seconds, remove the remaining liquid; A total of 3 samples; after the drug solution is dried, put into a straight tube of 10 cm long, access the 2nd instar larvae of Plutella xylostella, cover the tube with gauze; place the test in a standard processing room, 24 hours, 48 hours The test results were observed after 72 hours.

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

Table 4

The mortality levels in the table are: 100%-90% for Grade A; 90%-70% for Grade B; 70%-50% for Grade C; 50%-0% for Grade D.

Some compounds are more active than the reference drug Chlorantraniliprole, as shown in Table 5 below: ///〇6/-s/-8020si>l>d-slsosszM

Claims

Claim

A substituted phenylpyrazole amide derivative characterized by having the following general formula (I):

In the formula:

o

Z is H, halogen, amino, cyano, dC ₆ alkyl, dC ₆ alkoxy, dC ₆ alkylamino or z Y

; Y is 0, S or Η;

V is N or C; W is 0, S or N;

RH, halogen, nitro, dC ₆ alkyl, halogenated dC ₆ alkyl or dC ₆ alkoxy;

1 ² is 11, halogen, cyano, nitro, dC ₆ alkyl or halogenated dC ₆ alkyl;

R ³ is dC ₆ alkyl, ^dC ₆ alkyl, methylthio substituted alkyl, C ₂ -C ₆ alkenyl, ^ C ₂ -C ₆ fluorenyl, C ₂ -C ₆ alkynyl, 3⁄4 . ₂ -. ₆ alkynyl, methylthio substituted unsaturated hydrocarbon, C ₃ -C ₆ cycloalkyl or halogenated C ₃ -C ₆ cycloalkyl (excluding alkyl substituted by at least one C ₃ -C ₄ cycloalkyl) a substituted sulfonyl group, a substituted carbamoyl group, a substituted N-cyanosulfone (thio)imide or a benzyl group, wherein H on the benzyl ring may be further substituted by halogen, dC ₆ alkyl, halogenated dC ₆ alkyl;

R ⁴ is halogen, CF ₃ , CN, SOCF ₃ , S0 ₂ CF ₃ , SOCHF ₂ , S0 ₂ CHF ₂ , dC ₆ alkoxy, halogenated dC ₆ alkoxy, dC ₆ alkylthio, halogenated dC ₆ Alkylthio, C ₂ -C ₆ alkenyloxy, halogenated C ₂ -C ₆ decyloxy, C ₂ -C ₆ alkynyloxy, 3⁄4. ₂ -. ₆ alkynyloxy, C ₂ -C ₆ alkanoyloxy or C ₂ -C ₆ alkanoyloxy: R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ are H, halogen, N0 ₂ , CN, H ₂ , OH, dC ₆ alkyl, halogenated dC ₆ alkyl, C ₂ -C ₆ alkenyl, 3⁄4 generation. ₂ -. ₆ alkenyl, C ₂ -C ₆ alkynyl, 3⁄4 generation. ₂ -. ₆ alkynyl, C ₃ -C ₆ cycloalkyl or halo c ₃ -c ₆ cycloalkyl, dC ₄ alkylsulfinyl, halo dC ₄ alkylsulfinyl, dC ₄ alkylsulfonyl, halogen DC ₄ alkylsulfonyl, dC ₄ alkylamino, C ₂ -C ₈ dialkylamino, C ₃ -C ₆ trialkylsilyl, dC ₄ alkylthio or halogenated dC ₄ alkylthio, Meanwhile, when A is NH, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ cannot be H at the same time; R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ cannot be substituted by only one alkyl group or halogenated alkyl group. 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 ;}

The substituted phenylpyrazole amide derivative according to claim 1, wherein the halogen in the derivative is fluorine, chlorine, bromine or iodine; the alkyl group is a linear or branched alkyl group; a straight or branched alkyl group, the hydrogen atom on these alkyl groups may be partially or completely substituted by a halogen atom; the definitions of "haloalkenyl", "haloalkynyl" and "halocycloalkyl" The term "haloalkyl" is the same; alkenyl is straight or branched with 2 to 6 carbon atoms and may have a double bond at any position; alkynyl is a straight or branched chain having 2 to 6 carbon atoms There may be a triple bond at any position; the hetero atom in the five- or six-membered heterocyclic ring is Ν, Ο or S.

3. A process for the preparation of a substituted phenylpyrazole amide derivative according to claim 1, wherein the synthetic route is as follows:

The preparation steps are as follows: 1) Mixing the compound of the general formula II, an organic solvent and water, adding an oxidizing agent under stirring, and then reacting at a temperature of 0 ° C to a reflux temperature of the solvent for 0.5 to 48 hours, after filtering, removing the organic solvent under reduced pressure, using an alkali solution After alkalization to pH 12, the organic impurities are extracted with an organic solvent, and the aqueous phase is acidified to pH 1.5 to obtain the target compound III;

U

^ ^丫ΝΗ

The reaction is carried out for 0.5-48 hours to obtain the target compound I; when the hydrazine is S, the potassium thiocyanate is dissolved in an organic solvent, and the phase transfer catalyst polyethylene glycol-400 is added, stirred and dissolved, and reacted at room temperature for 0.5-4 hours. The insoluble matter in the reaction solution is filtered off to obtain a solution of the compound V, and the acid chloride IV is dissolved in an organic solvent, added dropwise to the solution of the compound V, and finally the mixed solution is mixed with the compound of the formula VI by a molar ratio of 1:1 at a temperature. It is 0 °. The reaction is carried out at a reflux temperature of the solvent for 2 to 12 hours to obtain a compound of the formula I.

The method for producing a substituted phenylpyrazole amide derivative according to claim 3, wherein the organic solvent is dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, cyclohexane , n-hexane, ethyl acetate, tetrahydrofuran, 1,4-dioxane, hydrazine, hydrazine-dimethylformamide or dimethyl sulfoxide.

The method for producing a substituted phenylpyrazole amide derivative according to claim 3, wherein the oxidizing agent is potassium permanganate, MCPBA, NaC10 ₂ , NaI0 ₄ /Ru0 ₂ H ₂ 0 ₂ or ozone.

The method for producing a substituted phenylpyrazole amide derivative according to claim 3, wherein the base is triethylamine, pyridine, 1,8-diaza-bicyclo(5,4,0) Undec-7-ene, hydrazine, hydrazine-dimethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium t-butoxide or potassium t-butoxide.

The method for producing a substituted phenylpyrazole amide derivative according to claim 3, wherein the acid is methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, phosphoric acid ester, hydrochloric acid , sulfuric acid or phosphoric acid.

The method for preparing a substituted phenylpyrazole amide derivative according to claim 3, wherein the mass ratio of the compound of the formula II, the organic solvent and the water in the step 1) is 1:2-50:2. The molar ratio of the compound of the formula II to the oxidizing agent is 1:3-11.

The method for preparing a substituted phenylpyrazole amide derivative according to claim 3, wherein the molar ratio of the compound of the formula III to the oxalyl chloride in the step 2) is 1:1.5-4, and the formula III The molar ratio of the compound to hydrazine, hydrazine-dimethylformamide (DMF) is from 1:0.05 to 0.15.

The method for preparing a substituted phenylpyrazole amide derivative according to claim 3, wherein the mass ratio of the acid chloride IV to the organic solvent in the step 3) is 1:2-50, the VI compound and the organic solvent The mass ratio is 1:2-50, the molar ratio of the acid chloride IV to the compound of the formula VI is 1:1, and the molar ratio of the acid chloride IV to the base is 1:1.5, the mass ratio of potassium thiocyanate to organic solvent is 1:10-80, the amount of polyethylene glycol-400 is 0.5-lwt% of organic solvent, and the molar ratio of acid chloride to potassium thiocyanate is 1: 2.5.

11. Use of a substituted phenylpyrazole amide derivative according to claim 1, characterized in that it is used for the preparation of agrochemical insecticides, in particular for the control of insects such as oriental armyworm and diamondback moth; It is also useful as a pesticidal composition which is active in the distribution of agriculturally acceptable auxiliaries for the control of insects.