WO2019128871A1 - N-alkyl-n-cyanoalkylbenzamide compound and use thereof - Google Patents

Abstract

Disclosed are an N-alkyl-N-cyanoalkylbenzamide compound: general formula (I), and an intermediate with general formula (II) used for preparing the compound, wherein: R1 is selected from halogen or C1-C3alkyl; R2 is selected from halogen or CN; R3 is selected from halogen and C1-C3haloalkyl; R4 is selected from halogen; R5 is selected from H or halogen; R6 is selected from C1-C3alkyl, C1-C3haloalkyl or C1-C5alkoxyalkyl; R7 is selected from C1-C5alkyl; and R8 is selected from hydrogen or C1-C5alkyl. Compared with compounds in the prior art, the compound of the general formula I of the present invention has a higher activity at low concentrations, particularly at concentrations below 1 ppm. The compound of the present invention has an insecticidal activity of more than 60%, greatly reducing the amount of compounds used in farmland and reducing the residue of compounds in farmland, which is conducive to protecting the environment.

Description

N-alkyl-N-cyanoalkylbenzamides and their applications Technical field

The invention relates to the field of insecticides, in particular to an N-alkyl-N-cyanoalkylbenzamide compound having insecticidal activity and application thereof.

Background technique

The problem of pest resistance has always been a problem for plant protection workers. To solve this problem, it is necessary to constantly seek new types of pesticides. The benzamides developed by DuPont are a new class of compounds targeting the nitinin receptor, representing the compound chlorantraniliprole (RynaxypyrTM), which exhibits excellent insecticidal activity and field Evaluation results, such as low toxicity to mammals and good environmental compatibility.

An N-cyanoalkyl anthranilamide compound is reported in the patent WO 2008134969, in which the compound 1.14 (KC1) has good insecticidal activity.

In the prior art, N-alkyl-N-cyanoalkylbenzamides as shown in the present invention are not disclosed.

Summary of the invention

The invention provides a novel N-alkyl-N-cyanoalkylbenzamide compound with higher insecticidal effect, which can be applied to the control of pests.

The technical scheme adopted by the present invention is as follows: a compound of the formula I N-alkyl-N-cyanoalkylbenzamide,

In formula I:

R _{1 is} selected from halogen or C ₁ -C ₃ alkyl; R _{2 is} selected from halogen or CN; R _{3 is} selected from halogen or C ₁ -C ₃ haloalkyl; R _{4 is} selected from halogen; and R _{5 is} selected from H or halogen. ; R _{6 is} selected from C ₁ -C ₃ alkyl, C1-C3 haloalkyl or C ₁ -C ₅ alkoxyalkyl; R _{7 is} selected from C ₁ -C ₅ alkyl; R _{8 is} selected from hydrogen or C ₁ - C ₅ alkyl. The physical properties of some of the compounds of the general formula I are shown in Figure 1; some of the compounds of the general formula I were subjected to nuclear magnetic resonance spectroscopy: ¹ H NMR: DMSO-d ₆ , 300 MHz The results obtained are shown in FIG.

Preferred compounds of the invention are those of formula I:

R _{1 is} selected from chlorine, bromine or methyl; R _{2 is} selected from chlorine, bromine, fluorine or CN; R _{3 is} selected from chlorine, bromine or trifluoromethyl; R _{4 is} selected from chlorine; and R _{5 is} selected from H or chlorine; R _{6 is} selected from the group consisting of C ₁ -C ₃ alkyl, CH ₂ OCH ₃ , CH ₂ O CH ₂ CH ₃ , CH ₂ CH ₂ OCH ₃ , CF ₃ , CH ₂ CH ₂ F, CH ₂ CHF ₂ , CH ₂ CF ₃ , CF ₂ CF ₃ or CF(CF ₃ ) ₂ ; R _{7 is} selected from methyl; R _{8 is} selected from hydrogen or methyl.

More preferred compounds are, in formula I: R _{1 is} selected from chlorine, bromine or methyl; R _{2 is} selected from chlorine, bromine, fluorine or CN; R _{3 is} selected from chlorine or bromine; R _{4 is} selected from chlorine; R ₅ It is selected from H; R _{6 is} selected from a methyl group; R _{7 is} selected from a methyl group; and R _{8 is} selected from a methyl group.

The invention also includes intermediates useful directly in the preparation of compounds of formula I, the structure of which is shown in Formula II:

In Formula II:

R _{1 is} selected from halogen or C ₁ -C ₃ alkyl; R _{2 is} selected from halogen or CN; R _{6 is} selected from C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₁ -C ₅ alkoxylated R _{7 is} selected from C ₁ -C ₅ alkyl; R _{8 is} selected from hydrogen or C ₁ -C ₅ alkyl. The physical properties of some of the compounds of formula II are shown in Figure 2.

Unless otherwise stated, the following terms used in the specification and claims have the meanings discussed below:

"Alkyl" means a saturated aliphatic hydrocarbon group, including both straight chain and branched forms, such as methyl, ethyl, propyl, isopropyl, and the like. "Haloalkyl" means a group wherein the alkyl group is substituted by one or more halogen atoms, such as chloroethyl, trifluoromethyl and the like. "Alkoxy" means a group having an oxygen atom bonded to the terminal of the alkyl group, such as methoxy, ethoxy, and the like.

The typical preparation of the present invention is as follows, but it is in no way intended to limit the scope of the invention in any way.

The compound of the formula I can be prepared by the reaction formula 1, wherein the substituent is as defined above unless otherwise specified.

Reaction formula 1:

The process of Scheme 1 comprises reacting a compound of formula II with a compound of formula III in the presence or absence of a base to provide a compound of formula I.

Adding an appropriate amount of a base substance is advantageous for the reaction, wherein the organic base is as follows: pyridine, triethylamine, potassium t-butoxide, 4-dimethylaminopyridine or N-methylmorpholine, and inorganic bases: sodium hydride, hydrogencarbonate Sodium, sodium carbonate, potassium carbonate, sodium hydroxide, and the like. The reaction is suitably carried out in an inert solvent such as tetrahydrofuran, acetonitrile, toluene, dichloromethane or the like.

After completion of the reaction, the reaction mixture containing the desired product is subjected to separation treatment according to an ordinary method, and if necessary, purification by recrystallization, column chromatography or the like, whereby the intended product can be obtained. These methods are well documented in the literature, for example, J. Org. Chem. 32, 3069 (1967) and the like.

The compound of the formula II can be prepared from the reaction formula 2, wherein the substituent is as defined above unless otherwise specified.

Reaction 2:

The compound represented by the general formula V is produced by a known method (for example, Organic Syntheses, 9, 32 (1929).), and a compound of the formula V is obtained by a commercially available acid chloride reagent such as thionyl chloride, oxalyl chloride or the like.

The compounds represented by the formula IV or IV' are partially commercially available and partly prepared by a known general method, for example, J. Am. Chem. Soc., 75, 4841-4842 (1953), Chemical Communications, 48 (50), 6253. -6255 (2012) and so on.

(1) Formula V → Formula VI

The compound of the formula VI can be obtained by reacting a compound of the formula V with a compound of the formula IV, which can be prepared by known methods, for example, J. Am. Chem. Soc., 135 (12), 4628-4631 (2013) and the like.

(2) Formula VI → Formula II

Typical methods include hydrogenation reduction in the presence of a metal catalyst such as Pd/C, platinum oxide or Ni in a hydroxyl solvent such as ethanol, methanol, isopropanol (eg Chinese Journal of Chemical Engineering, 24(9), 1195- 1200 (2016)). It can also be prepared by reduction of a metal such as zinc powder or iron powder under the catalysis of an acid. These methods are described in the literature, for example, WO 2010042699, Dye Industry, 37(4): 16-18 (2000) and the like.

In the organic molecule, after the hydrogen atom is replaced by a methyl group or other alkyl group, the fat solubility of the molecule can be improved. According to the analysis of the nuclear magnetic data, the introduction of the methyl group in the present invention causes the molecular to change in the spatial arrangement. . The fat solubility of molecules is closely related to the grooming of molecules in plants, insects and other organisms; the changes in molecular space structure also have an impact on the ability of molecules to bind to targets. These two points play an important role in the efficacy of drugs. The effects of molecular fat solubility and spatial structure on the bioactive molecular grooming properties and binding ability to the target are unpredictable and require a lot of creative labor to know.

It has now been found that the compounds of the formula I according to the invention have an unexpectedly high insecticidal activity compared to the known benzamidoacetonitriles, and therefore the invention also includes compounds of the formula I for use in the control. The use of pests.

The present invention also encompasses pesticidal compositions having a compound of formula I as an active ingredient. The active ingredient in the pesticidal composition is present in an amount between 1 and 99% by weight. Also included in the pesticidal composition are agricultural, forestry, and hygienic acceptable carriers.

The compositions of the invention may be administered in the form of a formulation. The compound of the formula I is dissolved or dispersed in the carrier as an active ingredient or formulated into a formulation for easier dispersion when used as an insecticide. For example, these chemicals can be formulated as wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.

The technical solution of the present invention also includes a method of controlling pests by applying the pesticidal composition of the present invention to the pest or the growth medium thereof. A more suitable effective amount is usually selected from 10 grams to 1000 grams per hectare.

For certain applications, for example, in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers, etc. may be added to the pesticidal composition of the invention, thereby producing additional The advantages and effects.

An advantage of the present invention is that the present invention discloses two compounds, the compound of the formula I has a higher activity at a lower concentration than the compound of the prior art, especially at a concentration of less than 1 ppm. The compound of the invention has more than 60% insecticidal activity, greatly reduces the amount of the compound used in the farmland, reduces the residue of the compound in the farmland, and protects the environment.

The compound of the formula II is an intermediate for the synthesis of the compound of the formula I, and the compound of the formula I and the formula II synthesized by the method of the invention has a short process route and a high yield; the invention provides a formula The new synthetic route of the compound of I solves the problem of inconvenient synthesis of similar compounds in the prior art, greatly reduces the production cost of the compound of the formula I, makes it more suitable for industrial applications, and reduces the production cost of the enterprise.

DRAWINGS

Figure 1 is a diagram showing the physical properties of a part of the compound of the formula I of the present invention;

Figure 2 is a diagram showing the physical properties of a compound of the formula II in the present invention;

Figure 3 is a schematic diagram showing the results of a nuclear magnetic resonance spectrum test of a compound of the formula I in the present invention: ¹ H NMR: DMSO-d ₆ , 300 MHz.

Detailed ways

The invention is further described in detail below with reference to specific embodiments, but is not intended to limit the invention.

Example 1

Compound 1.15: N-(6-N-((2-cyanopropyl-2-yl)-N-methylcarbamoyl)-2,4-dichlorophenyl)-1-(3-chloropyridine Synthesis of 2-yl)-3-bromo-1H-pyrazole-5-carboxamide

(1) Synthesis of 2-methyl-2-(methylamino)propionitrile

8.5 g (0.1 mol) of acetone cyanohydrin was added to a 50 ml four-necked flask, and 3.1 g (0.1 mol) of methylamine gas was slowly introduced at room temperature. After completion, the reaction was further stirred at room temperature for 5 hours. The organic phase was extracted with 10 ml of EtOAc (3 mL), dried over anhydrous sodium sulfate, and evaporated.

(2) Synthesis of 2-nitrobenzoyl chloride

8.4 g (0.05 mol) of 2-nitrobenzoic acid, 100 ml of dichloroethane, 17.8 g (0.15 mol) of thionyl chloride and 1 drop of DMF were sequentially added to a 250 ml single-mouth flask, and the temperature was raised to reflux. After reacting for 3 hours, it was desolvated under reduced pressure to obtain 8.9 g of a yellow liquid, yield 95.9%. Without further post-processing, use it directly in the next step.

(3) Synthesis of 2-nitro-N-methyl-N-(2-cyanopropan-2-yl)benzamide

4.9 g (0.05 mol) of 2-methyl-2-(methylamino)propionitrile, 20 ml of dichloromethane and 5.1 g (0.05 mol) of triethylamine were sequentially added to a 250 ml four-necked flask at 0 ° C. A solution of 8.9 g (0.048 mol) of 2-nitrobenzoyl chloride in 20 ml of dichloromethane was added dropwise, and after completion of the dropwise addition, the reaction was further stirred at 0 ° C for 2 h. After adding 50 ml of water to the reaction mixture, the mixture was extracted with EtOAc (EtOAc m. The yield was 76.6%.

Synthesis of (4) 2-Amino-N-methyl-N-(2-cyanopropan-2-yl)benzamide

20 ml of water, 2.2 g (0.04 mol) of reduced Fe powder and 1 ml of 30% hydrochloric acid were successively added to a 100 ml four-necked flask, slowly heated to 80 ° C, and further stirred at 80 ° C for 30 min, and then added in portions. 2.5 g (0.01 mol) of 2-nitro-N-methyl-N-(2-cyanopropan-2-yl)benzamide, the temperature is kept at not more than 80 ° C, after the addition, continue at 80 ° C The reaction was stirred and the HPLC was traced to completion. After the reaction solution was cooled to room temperature, 1.6 g of sodium hydroxide was added, followed by suction filtration, and the filter cake was washed with hot water. The collected filtrate was extracted with 2×100 ml of ethyl acetate. The organic phase was saturated with water, saturated sodium carbonate and saturated. After washing with brine, it was dried over anhydrous sodium sulfate and evaporated, and evaporated,

(5) Synthesis of N-(1-cyanoisopropyl)-N-methyl-2-amino-3,-5-dichlorobenzamide

1.1 g (5 mmol) of 2-amino-N-methyl-N-(2-cyanopropan-2-yl)benzamide, 2.2 g (12.5 mmol) of N-chlorosuccinimide and 20 ml of DMF was added to a 100 ml four-necked flask, and the reaction was stirred at room temperature, and the HPLC was traced to completion. The reaction mixture was poured into 100 ml of water, and extracted with 20 ml of ethyl acetate. The organic phase was combined, and the organic phase was washed sequentially with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate Solid, yield 78.6%.

(6) N-(6-N-((2-Cyanopropyl-2-yl)-N-methylcarbamoyl)-2,4-dichlorophenyl)-1-(3-chloropyridine Synthesis of 2-yl)-3-bromo-1H-pyrazole-5-carboxamide

1 g (0.00376 mol) of 2-amino-3,5-dichloro-N-methyl-N-(2-cyanopropan-2-yl)benzamide, 10 ml of tetrahydrofuran and 0.3 g (0.00376 mol) The pyridine was sequentially added to a 50 ml four-necked flask, and 1.2 g (0.00376 mol) of 2-(3-chloro-pyridin-2-yl)-5-bromo-2H-pyrazole-3 was slowly added dropwise under ice cooling. - 10 ml of a tetrahydrofuran solution of carbonyl chloride (prepared according to the method of WO 02/070483), after completion of the dropwise addition, the reaction was stirred overnight under an ice bath, and the progress of the reaction was followed by HPLC. The reaction solution was poured into 50 ml of water and extracted with dichloromethane (3×20 ml). The organic phase was washed successively with saturated sodium carbonate, saturated aqueous sodium chloride and water, dried over anhydrous sodium sulfate (eluent: ethyl acetate: petroleum ether = 3:1) gave 0.85 g of white solid.

Example 2

Compound 1.1: N-(2-N-((2-cyanopropyl-2-yl)-N-methylcarbamoyl)-4-chloro-6-methylphenyl)-1-(3- Synthesis of chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carboxamide

(1) Synthesis of 2-nitro-3-methylbenzoyl chloride

5.4 g (0.03 mol) of 2-nitro-3-methylbenzoic acid, 100 ml of dichloroethane, 23.8 g (0.2 mol) of thionyl chloride and 1 drop of DMF were sequentially added to a 250 ml single-mouth flask. The temperature was raised to reflux reaction, and after 3 hours of reaction, the solution was decomposed by pressure to obtain 5.7 g of a brown liquid in a yield of 95.2%. Without further post-processing, use it directly in the next step.

Synthesis of (2), N-(1-Cyanoisopropyl)-N-methyl-3-methyl-2-nitrobenzamide

4.0 g (0.03 mol) of 2-methyl-2-(methylamino)propionitrile hydrochloride, 10 ml of tetrahydrofuran, 10 ml of water and 5.1 g (0.06 mol) of NaHCO ₃ were sequentially added to a 250 ml four-necked flask. A solution of 5.7 g of 2-nitro-3-methylbenzoyl chloride in 20 ml of tetrahydrofuran was added dropwise at -10 ° C, and after completion of the dropwise addition, the reaction was further stirred at -10 ° C for 2 h. After adding 50 ml of water to the reaction mixture, the mixture was extracted with EtOAc (EtOAc m. The yield was 56.5%.

Synthesis of (3), N-(1-Cyanoisopropyl)-N-methyl-3-methyl-2-aminobenzamide

20 ml of water, 2.2 g (0.04 mol) of reduced Fe powder and 1 ml of 30% hydrochloric acid were successively added to a 100 ml four-necked flask, slowly heated to 80 ° C, and stirred at 80 ° C for 30 min, and then added in portions. 2.6g (0.01mol) of N-(1-cyanoisopropyl)-N-methyl-3-methyl-2-nitrobenzamide, the temperature is kept at not more than 80 ° C, after the addition, continue The reaction was stirred at 80 ° C and the HPLC was traced to completion. After the reaction solution was cooled to room temperature, 1.6 g of sodium hydroxide was added, followed by suction filtration, and the filter cake was washed with hot water. The collected filtrate was extracted with 2×100 ml of ethyl acetate. The organic phase was saturated with water, saturated sodium carbonate and saturated. After washing with brine, it was dried over anhydrous sodium sulfate and evaporated to dryness.

Synthesis of (4), N-(1-Cyanoisopropyl)-N-methyl-2-amino-3-methyl-5-chlorobenzamide

1.6 g (6.9 mmol) of N-(1-cyanoisopropyl)-N-methyl-3-methyl-2-aminobenzamide, 1.4 g (10.3 mmol) of N-chlorobutane The imide and 20 ml of DMF were placed in a 100 ml four-necked flask, and the reaction was stirred at room temperature, and the HPLC was traced to completion. The reaction mixture was poured into 100 ml of water, and extracted with 20 ml of EtOAc (3 mL). Yellow solid, yield 83.1%.

(5), N-(2-N-((2-cyanopropyl-2-yl)-N-methylcarbamoyl)-4-chloro-6-methylphenyl)-1-(3) Synthesis of -chloropyridin-2-yl)-3-bromo-1H-pyrazole-5-carboxamide

0.3 g (1 mmol) of N-(1-cyanoisopropyl)-N-methyl-2-amino-3-methyl-5-chlorobenzamide, 10 ml of dichloromethane, 0.1 g (1 mmol) Triethylamine and 0.32 g (1 mmol) of 2-(3-chloro-pyridin-2-yl)-5-bromo-2H-pyrazole-3-carbonyl chloride (prepared according to the method of WO 02/070483) are sequentially added to The mixture was stirred at room temperature in a 50 ml single-necked flask and traced to completion by HPLC. The reaction solution was poured into 50 ml of water and extracted with dichloromethane (3×20 ml). The organic phase was washed successively with saturated sodium carbonate, saturated aqueous sodium chloride and water, dried over anhydrous sodium sulfate (eluent: ethyl acetate: petroleum ether = 3:1) afforded 0.20 g of white solid.

Example 3

Compound 1.6: N-(2-N-((2-cyanopropyl-2-yl)-N-methylcarbamoyl)-4-cyano-6-methylphenyl)-1-(3) Synthesis of -chloropyridin-2-yl)-3-chloro-1H-pyrazole-5-carboxamide

(1) 2-Amino-3-methyl-5-iodo-N-(1-cyanoisopropyl)-N-methylbenzamide

76.3 g (0.33 mol) of N-(1-cyanoisopropyl)-N-methyl-3-methyl-2-aminobenzamide and 250 ml of DMF were sequentially added to a 500 ml four-necked flask. 78.2 g (0.35 mol) of N-iodosuccinimide was slowly added under stirring at room temperature. After the addition, the reaction was heated to 75 ° C, and the HPLC was traced to completion. The reaction solution was poured into 500 ml of water to precipitate a large amount of solid, and suction-dried, dried lavender powder solid 69.1 g, yield 58.6%.

(2) Synthesis of 2-amino-3-methyl-5-cyanobenzoic acid

60 g (0.17 mol) of 2-amino-3-methyl-5-iodo-N-(1-cyanoisopropyl)-N-methylbenzamide, 33 g (0.37 mol) of CuCN and 300 ml were successively The DMF was sequentially added to a 500 ml four-necked flask, and the temperature was raised to 145 ° C for reaction, and the HPLC was traced to completion. After most of the solvent was desolvated, 720 ml of water and 15.8 g of ethylenediamine were added, and after insoluble matter was removed by suction filtration, 64 g of 30% hydrochloric acid was slowly added to the filtrate to adjust the pH to a weak acidity, and a large amount of The white solid precipitated, suction filtered, and the cake was dried to yield 18.8 g of a white solid.

(3) Synthesis of 3-chloro-2-pyridinium

185 g (1.25 mol) of 2,3-dichloropyridine was added to 800 mL of n-butanol, followed by the addition of 315 g of hydrazine hydrate, and the temperature was raised to reflux for 35-40 h, cooled to room temperature, filtered, and dried to give white crystals, 120 g, yield 66.9%. .

Synthesis of (4), 2-(3-Chloro-2-pyridyl)-5-carbonylpyrazolone-3-carboxylic acid ethyl ester

24 g (1.04 mol) of crushed sodium was added to 920 g of absolute ethanol in portions, and the temperature was naturally raised to reflux. After the sodium is completely dissolved, it is cooled to below 40 ° C, 120 g of 3-chloro-2-pyridinium (0.836 mol) is added in one portion, and the temperature is maintained at 40 to 45 ° C, and 210 g (1.22 mol) of diethyl maleate is added dropwise, 1 hour. Finish. The reaction was continued at 40 to 45 ° C for 4 h, cooled to room temperature, and poured into a cold aqueous solution of glacial acetic acid with stirring, and 650-700 mL of ethanol was distilled off under reduced pressure, cooled to room temperature, allowed to stand, and filtered, and the filter cake was 65 mL × 2 The mixture was washed with ethanol, and the cake was collected and dried to obtain 120 g of a finished product. The filtrate and the washing liquid were combined, and almost all the ethanol was concentrated under reduced pressure to obtain a large amount of dark green solution with a black solid. The solution was extracted with chloroform (200 mL), dried over anhydrous magnesium sulfate, filtered, and concentrated to dryness. After cooling to room temperature, the refrigerator was frozen overnight, filtered, washed with 15 mL of toluene, and dried to obtain 9 g of dark green solid recovered, the total yield was 57.2%.

Synthesis of (5), 3-Chloro-1-(3-chloro-2-pyridyl)-4,5-dihydropyrazole-5-carboxylic acid ethyl ester

109.8 g (0.716 mol) of phosphorus oxychloride was added to 430 g of acetonitrile, followed by the addition of 134.5 g (0.499 mol) of 2-(3-chloro-2-pyridyl)-5-carbonylpyrazolone-3-carboxylic acid The ester was heated to a refluxing reaction for 4 to 5 hours. The reaction solution was poured into 1200 g of ice water, extracted twice with 400 mL of chloroform, and then washed once with 300 mL of 10% aqueous sodium hydrogencarbonate. The organic phase was separated and dried over anhydrous sodium sulfate for 5h. Concentrate under reduced pressure to near dryness. Add 200 mL of absolute ethanol, heat to 60 ° C, stir well, remove by heat, freeze at -18 ° C overnight, filter, wash with absolute ethanol, and dry to obtain 113.7 g of light purple crystal, the yield is 79.1%.

Synthesis of (6), 3-Chloro-1-(3-chloro-2-pyridyl)-pyrazole-5-carboxylic acid ethyl ester

110.1 g (0.382 mol) of ethyl 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydropyrazole-5-carboxylate was added to 910 mL of acetonitrile, stirred until dissolved, and added to a thick 65.1 g (0.664 mol) of sulfuric acid, followed by adding 181 g of potassium persulfate (0.67 mol) to reflux, stirring and refluxing for 15 h, cooling, pouring into 1500 g of ice water, extracting twice with 500 mL of chloroform, washing with 100 mL of 10% sodium hydrogencarbonate, anhydrous The residue was dried (MgSO4), filtered

Synthesis of (7), 3-Chloro-1-(3-chloro-2-pyridyl)-pyrazole-5-carboxylic acid

57.2 g (0.2 mol) was suspended in 850 g of ethanol, and the temperature was raised to 50 ° C, and a solution of 28.6 g (0.511 mol) of potassium hydroxide in 250 mL of water was added dropwise thereto, and the addition was completed for 30 minutes. The reaction was kept at 50-55 ° C for 5 h, all ethanol was concentrated under reduced pressure, 300 mL of water was added, the mixture was cooled to room temperature, ethyl acetate (100 mL) was extracted, and the aqueous phase was evaporated under reduced pressure to dryness ethyl ether, cooled to room temperature, and slowly added dropwise with stirring. 15% hydrochloric acid to the solution pH=2, stirring was continued for 2 h, filtered, washed with water and dried to give 46.1 g of pale yellow solid.

Synthesis of (10), 3-bromo-1-(3-chloro-2-pyridyl)-pyrazole-5-carbonyl chloride

30 g (0.33 mol) of 3-chloro-1-(3-chloro-2-pyridyl)-pyrazole-5-carboxylic acid was suspended in 1500 mL of dichloromethane, and 1 mL of DMF was added, and 63 g (0.496 mol) of grass was added in about 4 h. The acid chloride was added dropwise to the above suspension, and the reaction was stirred overnight to obtain a clear solution, which was concentrated to dryness under reduced pressure to give a semi solid.

(11), N-(2-N-((2-Cyanopropyl-2-yl)-N-methylcarbamoyl)-4-cyano-6-methylphenyl)-1-( Synthesis of 3-chloropyridin-2-yl)-3-chloro-1H-pyrazole-5-carboxamide

0.26 g (1 mmol) of N-(1-cyanoisopropyl)-N-methyl-3-methyl-2-amino-5-cyanobenzamide, 10 ml of acetonitrile and 0.1 g (1 mmol) The triethylamine was sequentially added to a 50 ml single-necked flask, heated to reflux, and 0.28 g (1 mmol) of 2-(3-chloro-pyridin-2-yl)-5-chloro-2H was added in one portion at reflux temperature. 2-pyridine solution of pyrazole-3-carbonyl chloride in 2 ml of acetonitrile, the reaction was stirred at reflux temperature and the HPLC was followed until the end of the reaction. The reaction solution was poured into 50 ml of water, and extracted with dichloromethane 3*20 ml. The organic phase was washed successively with saturated sodium carbonate, saturated aqueous sodium chloride and water, dried over anhydrous sodium sulfate (eluent: ethyl acetate: petroleum ether = 3:1) gave 0.28 g of white solid.

Biological activity assay

The test agents were all dissolved in a 1000 mg/L solution using a mixture of acetone: N`N'-dimethylformamide. 1% Tween-80 was added as an emulsifier to each of the drug solutions. These solutions were then diluted to the desired concentration of test solution with 1% Tween-20 aqueous solution. An aqueous solution containing 1% Tween-20 was used as a control.

Example 4: Insecticidal effect on beet armyworm

The amaranth leaves were punched into a 1cm diameter leaf disc with a puncher and sprayed with Airbrush. A certain concentration of the test compound was sprayed on the front and back of each leaf disc, and the amount of liquid sprayed was 0.5 ml. After the dry operation, 10 shots per treatment were applied. Insects (3rd instar larvae) were treated three times per treatment. After treatment, they were placed at 25 ° C, relative humidity of 60% to 70%, and cultured in the absence of light. After 120 hours, the number of surviving insects was investigated and the mortality was calculated.

When the concentration of the chemical solution is 10 ppm, some compounds such as 1.1, 1.15, 1.23, 1.32 and 1.33 have better control effects on beet armyworm, reaching 80% or more.

Example 5: Insecticidal effect on Spodoptera litura

The leaves of the leek that have not been exposed to the insecticide are made of scissors and about 40mm square leaves. These leaves are immersed in the solution of each compound for 30s, the leaves are placed on the absorbent paper, and air-dried to the leaves. Obvious water stains. Place the leaf dish after the dipping in a Petri dish (7 cm) and place 3 leaf discs per dish. The 3rd instar larvae of Spodoptera litura, which were raised from the indoor amaranth seedlings, were gently picked up on a leaf dish placed on a petri dish with a writing brush, and 10 to 15 worms were placed in each dish. The larvae were covered with a petri dish cover and placed in a larvae room at 25 ° C. The light was exposed for 16 h/dark for 8 h. After 120 h, the number of viable worms was investigated and the mortality was calculated.

Some test results are as follows:

When the concentration of the drug solution was 4 ppm, some compounds such as 1.1, 1.9, 1.15, 1.23, 1.32 and 1.33 had a mortality rate of more than 80% against the 3rd instar larvae of Spodoptera litura.

When the concentration of the drug solution was 1 ppm, some compounds such as 1.1, 1.9, 1.15 and 1.23 had a mortality rate of more than 80% against the 3rd instar larvae of Spodoptera litura.

Example 6: Insecticidal effect on cotton bollworm

The prepared fresh amaranth leaf disc is immersed in a certain concentration of the test compound liquid solution for 10 seconds, and taken out and naturally dried. A 24-well plate was used, and one tablet was placed in each well. At the same time, a third-instar cotton bollworm larva was inserted and moisturized. After 120 hours, the number of surviving insects was investigated and the mortality was calculated.

Some test results are as follows:

When the concentration of the chemical solution is 4 ppm, some compounds such as 1.1, 1.15, 1.32 and 1.33 have a mortality rate of more than 80% for the 3rd instar cotton bollworm larvae.

When the concentration of the drug solution is 1 ppm, some compounds such as 1.1, 1.5, 1.15 and 1.33 have a mortality rate of more than 80% for the 3rd instar cotton bollworm larvae.

Example 7: Insecticidal effect on rice leaf roller

After the roots of the rice seedlings that have not been exposed to the insecticide are pulled out, the roots are washed, and the stems and leaves of the seedlings are immersed in the liquid of different concentration of the drug after the leaves have no obvious water stains (the liquid is contained in the test tube, the stem The leaves are immersed in it); after 30s of immersion, they are taken out and placed on absorbent paper to dry to the leaves without water stains. Filter the paper in a Petri dish (7 cm), moisten with water and invert the Petri dish until no water droplets flow out; cut the seedlings of the infiltrated leaves into leaves of the same diameter as the Petri dish, and lay the leaf sections on the Petri dish On the filter paper, place 15 to 20 leaf segments per petri dish.

Three to four-year-old rice leaf roller larvae raised from indoor wheat seedlings were gently picked up on the leaf sections of the petri dish with a writing brush, and 10 dishes were received per dish. The cover of the petri dish was placed on the back of the incubator and placed in a temperature incubator at 25 ° C for 16 h / dark for 8 h. The death of Cnaphalocrocis medinalis was investigated 72h after inoculation.

Some test results are as follows:

When the concentration of the chemical solution is 20 ppm, some compounds such as 1.1, 1.9, 1.15, 1.23, 1.32 and 1.33 have a mortality rate of more than 80% for 3 to 4 years old rice leaf roller.

When the concentration of the chemical solution is 10 ppm, some compounds such as 1.1, 1.15 and 1.32 have a mortality rate of more than 80% for 3 to 4 years old rice leaf roller.

Example 8: Insecticidal effect on Plutella xylostella

Three-year-old Plutella xylostella larvae were selected Select amaranth, wash and dry, use a puncher to make a leaf dish, dip in the liquid for 10 seconds, and then dry it naturally and put it into the dish. 10 dishes of 3rd instar larvae of Plutella xylostella were added to each dish and repeated 3 times. The number of dead insects in 3 days was investigated and the mortality was counted.

Some test results are as follows:

When the concentration of the drug solution is 1 ppm, some compounds such as 1.1, 1.9, 1.15, 1.23, 1.24, 1.28 to 1.30, 1.32 and 1.33 have a mortality rate of more than 90% against Plutella xylostella.

According to the above method, the comparative compound KC1 (compound 1.14 in WO 2008134969) and KC2 (compound 1.18 in WO 2008134969) which are structurally closest to the compound of the present invention are selected for parallel determination of Plutella xylostella, and the experimental results are obtained. As shown in the table below.

Parallel comparison of the activity of the compound 1.15 of the present invention with the known compounds KC1 and KC2 against Plutella xylostella (% mortality)

It can be seen from the above table that the compound KC1 and the compound KC2 disclosed in the prior art have a higher activity in the killing process of Plutella xylostella at a concentration of less than 1 ppm, compared with KC1 and The KC2 test results show that the compound is applied in a smaller amount, but its activity is higher.

The structural formula of KC2 is as follows:

Claims (8)

An N-alkyl-N-cyanoalkylbenzamide compound of the formula I,

among them: R _{1 is} selected from halogen or C ₁ -C ₃ alkyl; R _{2 is} selected from halogen or CN; R _{3 is} selected from the group consisting of halogen, C ₁ -C ₃ haloalkyl; R _{4 is} selected from halogen; R _{5 is} selected from H or halogen; R _{6 is} selected from C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₁ -C ₅ alkoxyalkyl; R _{7 is} selected from C ₁ -C ₅ alkyl; R _{8 is} selected from hydrogen or C ₁ -C ₅ alkyl. The N-alkyl-N-cyanoalkylbenzamide compound according to claim 1, wherein a preferred compound of the formula I: R _{1 is} selected from chlorine, bromine or methyl; R _{2 is} selected from the group consisting of chlorine, bromine, fluorine or CN; R _{3 is} selected from chlorine, bromine or trifluoromethyl; R _{4 is} selected from chlorine; R _{5 is} selected from H or chlorine; R _{6 is} selected from the group consisting of C ₁ -C ₃ alkyl, CH ₂ OCH ₃ , CH ₂ OCH ₂ CH ₃ , CH ₂ CH ₂ OCH ₃ , CF ₃ , CH ₂ CH ₂ F, CH ₂ CHF ₂ , CH ₂ CF ₃ , CF ₂ CF ₃ or CF(CF ₃ ) ₂ ; R _{7 is} selected from a methyl group; R _{8 is} selected from hydrogen or methyl. The N-alkyl-N-cyanoalkylbenzamide compound according to claim 1, wherein a preferred compound of the formula I: R _{1 is} selected from chlorine, bromine or methyl; R _{2 is} selected from the group consisting of chlorine, bromine, fluorine or CN; R _{3 is} selected from chlorine or bromine; R _{4 is} selected from chlorine; R _{5 is} selected from H; R _{6 is} selected from a methyl group; R _{7 is} selected from a methyl group; R _{8 is} selected from a methyl group. An intermediate for the preparation of the N-alkyl-N-cyanoalkylbenzamide compound of claim 1, wherein the intermediate compound is as shown in Formula II:

Wherein R _{1 is} selected from halogen or C ₁ -C ₃ alkyl; R _{2 is} selected from halogen or CN; R _{6 is} selected from C ₁ -C ₃ alkyl, C ₁ -C ₃ haloalkyl or C ₁ -C ₅ alkoxyalkyl; R _{7 is} selected from C ₁ -C ₅ alkyl; R _{8 is} selected from hydrogen or C ₁ -C ₅ alkyl. A method of preparing a compound of formula I according to claim 4, wherein the method is as follows: The compound of the formula II is reacted with a compound of the formula III to give a compound of the formula I, the reaction formula being as follows:

among them: R _{3 is} selected from the group consisting of halogen, C ₁ -C ₃ haloalkyl; R _{4 is} selected from halogen; R _{5 is} selected from H or halogen. Use of a compound of formula I according to claim 1 or 2 or 3 for the preparation of insecticides for controlling pests. A pesticidal composition comprising a compound of formula I according to claim 1 and an agricultural, forestry, hygienic acceptable carrier, wherein the active ingredient is present in the composition in an amount of from 0.1 to 99.5% by weight. A method for controlling pests, characterized in that the pesticidal composition according to claim 7 is applied to a growth medium of pests or pests at an effective dose of 10 g/hm ² to 1000 g/hm ² .

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