A pyrazolohexane-5-carboxamide compound containing an aryl (or) acylamide group, and a preparation method and application thereof

Abstract

The application discloses a pyrazole hexacyclic-5-formamide compound containing an aromatic (ethyl) amide group and a preparation and application thereof. A structural general formula of the compound is shown as formula I. The compound is prepared through an amide condensation reaction, and the preparation method is simple. The pyrazole hexacyclic-5-formamide compound containing the aromatic (ethyl) amide group has an obvious inhibiting effect on growth and development of agricultural pests and growth and development of monocotyledonous or dicotyledonous plants. After application, the pests show symptoms of individual atrophy, skin wrinkling, abnormal molting of insect body deformity and even death, and the plants show that the growth of roots and stems is inhibited. The formula I compound can be applied in agriculture as an insecticide and / or herbicide.

Description

Technical Field

[0001] This invention belongs to the field of agricultural chemicals, specifically relating to a pyrazolium-5-carboxamide compound containing an aromatic (acetamide) group, its preparation method, and the application of this type of compound in pest control and weeding. Background Technology

[0002] Pesticides are a powerful tool for ensuring food security, reducing crop losses caused by pests, diseases, and weeds, thereby significantly increasing grain yield and quality. However, the irrational use of traditional pesticides has led to negative consequences such as pesticide residues, resistance, and environmental pollution. To address these issues, the development of eco-friendly new pesticides is urgently needed. In the pesticide field, creating pesticides with both insecticidal and herbicidal activities is extremely rare because the targets of pests and weeds vary greatly. Therefore, exploring such multifunctional pesticides is of great value and significance.

[0003] Nitrogen heterocyclic compounds are diverse and possess advantages such as insecticidal, fungicidal, herbicidal, and plant growth-regulating activities, making them a key focus of new pesticide research and development. Pyrazole compounds, as an important class of heterocyclic compounds, hold a particularly important position in the field of new drug development. Pyrazole compounds have advantages such as high efficiency, low toxicity, high selectivity, and structural diversity, aligning with the development concept and requirements of modern green pesticides. Therefore, among the currently developed new pesticide varieties, an increasing number of pyrazole insecticides, acaricides, fungicides, and herbicides have emerged, such as fipronil, acetamiprid, cyclopropamide, bromocyanamide, ethoxyfenozide, fluoxastrobin, pyraclostrobin, pyrazosulfuron, pyrazosulfuron-methyl, and pyrazosulfuron-methyl. However, with the widespread use of these agents, resistance problems are becoming increasingly prominent, making the development of novel pyrazole pesticide varieties both necessary and urgent.

[0004] Pyrazole amide compounds have a wide range of physiological activities, including insecticidal, herbicidal, antibacterial, and antiviral effects. They are an important intermediate in the synthesis of organic drugs and are widely used in various fields such as insecticides, herbicides, fungicides, and plant growth regulators.

[0005] Patent CN111574452B discloses the following general structural formula A and specific compounds A-13 and A-14, which have good insecticidal activity against diamondback moth.

[0006]

[0007] Patent CN105367498B discloses the following general structural formula B and specific compounds B-2 and B-4, which have good insecticidal activity against armyworm, Asian corn borer, cotton bollworm and diamondback moth.

[0008]

[0009] Patent WO9405642A1 discloses the following general formula C and specific compound C-7, which have certain insecticidal activity against tobacco shoot moth and also have certain control effects against tomato Phytophthora root rot.

[0010]

[0011] Patent GB2149402A discloses the following general structural formula D and specific compound D-1, which is suitable for pre-emergence or post-emergence treatment of weeds and has a good control effect on weeds.

[0012]

[0013] Patent CN109169693B discloses the following general structural formula E and specific compound E-2, which showed good herbicidal activity against two weeds: lettuce and creeping bentgrass.

[0014]

[0015] However, there are relatively few pyrazole amide compounds with the above-mentioned activities, especially in terms of pesticide activity, there are even fewer pyrazole amide pesticides that have both insecticidal and herbicidal activities. Summary of the Invention

[0016] The purpose of this invention is to provide a pyrazolium-5-carboxamide compound containing an aromatic (acetamide) group, its preparation method, and its application. The pyrazolium-5-carboxamide compound containing an aromatic (acetamide) group of this invention has a significant inhibitory effect on the growth and development of agricultural pests and monocotyledonous or dicotyledonous plants. After application, pests exhibit symptoms such as individual shrinkage, epidermal wrinkling, abnormal molting, and even death. Plants show inhibited root and stem growth and can be used as an insecticide and / or herbicide in agriculture.

[0017] The pyrazolhexane-5-carboxamide compound containing an aromatic (acetamide) group provided by this invention has the structural formula shown in Formula I below:

[0018]

[0019] In formula I,

[0020] n is an integer from 0 to 3;

[0021] R is selected from hydrogen, halogen, substituted or unsubstituted phenyl, cyclopropyl, cyclohexyl, C1-C6 alkyl, C1-C4 alkoxy, halo-C1-C4 alkyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C1-C4 alkyl carbonyl, and halo-C1-C4 alkyl carbonyl; wherein the substituted phenyl contains one or more substituents, each of which is independently selected from at least one of hydrogen, halogen, amino, hydroxyl, nitro, cyano, C1-C6 alkyl, C1-C4 alkoxy, and halo-C1-C4 alkyl.

[0022] Specifically, the compound represented by Formula I is a compound represented by the following general formula:

[0023]

[0024] n is an integer from 0 to 3;

[0025] R1 represents a substituent on the benzene ring, which can be monosubstituted or polysubstituted;

[0026] R1 is independently selected from: H, halogen, C1-C6 alkyl, C1-C4 alkoxy, and halogenated C1-C4 alkyl;

[0027] Specifically, R1 is independently selected from: H, fluorine, chlorine, bromine, methyl, methoxy, tert-butyl, and trifluoromethyl;

[0028] More specifically, R1 represents at least one of 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-bromo, 3-bromo, 4-bromo, 2-methyl, 3-methyl, 4-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 4-tert-butyl, 4-trifluoromethyl, 3,4-dimethyl, 3,4-difluoro, and 2,6-difluoro.

[0029] The pyrazolohexane-5-carboxamide compound containing an aryl (acetyl) group shown in Formula I above can be any one of the following:

[0030]

[0031] The present invention also provides a method for preparing the compound shown in Formula I above.

[0032] The preparation method of the compound shown in Formula I includes the following steps: in an organic solvent, the compound shown in Formula II and the compound shown in Formula III undergo an amide condensation reaction to obtain the compound shown in Formula I.

[0033]

[0034] In Equation III, n is the same as in Equation I; R is the same as in Equation I.

[0035] In the above preparation method, the organic solvent is selected from at least one of dichloromethane, ethyl acetate, petroleum ether, methanol, ethanol, n-propanol, carbon tetrachloride, DMF, tetrahydrofuran, chloroform, diethyl ether, and acetonitrile.

[0036] The amidation reaction also involves the addition of a condensation reagent to activate the carboxyl group in the compound shown in Formula II.

[0037] The condensation reagent is at least one of DCC, DMAP, DIC, DIEA, EDCI, and HOBt.

[0038] In the above preparation method, the temperature of the amide condensation reaction can be 0-60°C, preferably room temperature, and the time can be 1-24 hours, preferably 8 hours, 12 hours or 12-16 hours.

[0039] The molar ratio of the compound shown in Formula II to the compound shown in Formula III can be 1:1 to 3, specifically 1:1.2 or 1:1.2 to 3.

[0040] The compound shown in Formula II was prepared according to the following route:

[0041]

[0042] Its preparation method includes the following steps:

[0043] 1) Cyclohexanone, diethyl oxalate, sodium ethoxide, and an organic solvent are mixed, with the molar ratio of cyclohexanone to diethyl oxalate being 1:1, 1:1-3, or 1:1-4, and reacted at -5℃ to 10℃ to obtain the compound shown in formula (2); the organic solvent is one or more of methanol, ethanol, toluene, xylene, tetrahydrofuran, and n-propanol.

[0044] 2) The compound shown in formula (2) and phenylhydrazine hydrochloride are mixed with an organic solvent, the molar ratio of the compound shown in formula (2) to phenylhydrazine hydrochloride is 1:0.8 to 3, the pH of the reaction mixture is controlled at 6 to 9, and the reaction is carried out at -10℃ to 30℃ to obtain the compound shown in formula (3); the acid-binding agent used to control the pH is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine; the organic solvent is one or more of methanol, ethanol, dichloromethane, acetone, chloroform and acetonitrile;

[0045] 3) The compound shown in formula (3) is mixed with an inorganic base and hydrolyzed. After the reaction is complete, the compound is placed in ice water, and the pH is adjusted to 2-3 with hydrochloric acid. The mixture is filtered using a Buchner funnel, and the filter cake is the compound shown in formula (4). The hydrolysis conditions are 60-100℃ and 0.5-12h. The inorganic base is one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0046] 4) The compound shown in formula (4) is mixed with an acyl chloride reagent to carry out an acyl chloride reaction to obtain the compound shown in formula (5). The molar ratio of the compound shown in formula (4) to the acyl chloride reagent can be 1:1-3, specifically 1:1; 1:1.5; 1:2. The acyl chloride reagent is one of dichlorosulfuron, phosphorus oxychloride, phosphorus pentachloride, and oxalyl chloride, specifically oxalyl chloride.

[0047] 5) Under acid-binding conditions, the compound shown in formula (5) is mixed with glycine ethyl ester hydrochloride in an organic solvent, wherein the molar ratio of the compound shown in formula (5) to glycine ethyl ester hydrochloride is 1:1, 1:1-3 or 1:1-4, and the mixture is reacted at -5℃ to 25℃ to obtain the compound shown in formula (6); the organic solvent is one of dichloromethane and acetonitrile; the acid-binding agent used is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and triethylamine, specifically triethylamine;

[0048] 6) The compound shown in formula (6) is hydrolyzed under the conditions of methanol and inorganic base. After the reaction is completed, the mixture is concentrated, an appropriate amount of ice water is added, and the pH is adjusted to 2-3 with 5% dilute hydrochloric acid. The mixture is filtered, and the filter cake is the compound shown in formula II. The hydrolysis conditions are 10-25℃ and 2-12h. The inorganic base is one or more of sodium hydroxide, potassium hydroxide, and lithium hydroxide.

[0049] The application of the compound shown in Formula I above in the control of agricultural pests and weeds is also within the scope of protection of this invention.

[0050] In the above applications, the pests can be lepidopteran pests, specifically including diamondback moth, Asian corn borer, fall armyworm, etc.

[0051] In the above applications, the weeds can be dicotyledonous or monocotyledonous weeds, specifically including Arabidopsis thaliana, ryegrass, etc.

[0052] The present invention also provides an insecticide.

[0053] The insecticide contains the compound shown in Formula I above or uses the compound shown in Formula I as the active ingredient;

[0054] The insecticide can kill agricultural pests, which may be lepidopteran pests, specifically diamondback moth, Asian corn borer, fall armyworm, etc.

[0055] The present invention also provides a herbicide.

[0056] The herbicide contains the compound shown in Formula I above or uses the compound shown in Formula I as the active ingredient;

[0057] The grasses mentioned are dicotyledonous or monocotyledonous weeds, specifically Arabidopsis thaliana, ryegrass, etc.

[0058] The insecticide and / or herbicide also contain excipients, which are reagents commonly used in the art, specifically DMSO, acetone, and DMF.

[0059] The present invention has the following advantages:

[0060] The pyrazol-5-carboxamide compounds containing aryl (acetyl) groups prepared by this invention have novel structures, and some compounds have both excellent insecticidal and herbicidal activities, and can be used as insecticides and / or herbicides in agriculture. Detailed Implementation

[0061] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0062] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0063] Example 1: Preparation of compound I-09 as an example

[0064]

[0065] The preparation of compound (2) was carried out according to the literature (Molecules 2023, 28(9), 3741), and the specific steps were as follows: Compound (1) (7.26 g, 0.074 mol) and diethyl oxalate (10.81 g, 0.074 mol) were added dropwise to 55 mL of an ethanol solution containing sodium ethoxide (2.52 g, 0.037 mol), and the reaction was carried out at 0 °C. The mixture was stirred at room temperature (25 °C) for 5 h. After 5 h, the mixture was acidified and filtered to remove the filter cake. The filtrate was extracted with dichloromethane, dried, concentrated under vacuum, and purified by column chromatography to obtain an orange-red viscous liquid compound (2) (10.56 g; 72%). 1 H NMR (300MHz, DMSO) δ4.26–4.16(m,2H),3.51–3.30(m,1H),2.35(t,J=6.2Hz,2H),2.17(t,J=5.7Hz,2H),1.71–1.51(m,4H),1.30–1.21(m,3H).

[0066] The preparation of compound (3) was carried out according to reference (CN111574452B), and the specific steps were as follows: Phenylhydrazine hydrochloride (6.07 g, 0.042 mol) was dissolved in 70 mL of anhydrous ethanol. The pH of the solution was adjusted to 7 with TEA, and a mixture of compound (2) (8.33 g, 0.042 mol) and 50 mL of ethanol was slowly added dropwise at room temperature. After the addition was complete, the mixture was stirred overnight at room temperature. The resulting cooled mixture was concentrated under vacuum and purified by column chromatography to obtain a red solid (3) (6.36 g; 56%). 1 H NMR (300MHz, CDCl3) δ7.49–7.36(m,5H),4.24(q,J=7.1Hz,2H),2.85(t,J=5.9Hz,2H),2.78(t,J=5.9Hz,2H),1.95–1.76(m,4H),1.23(t,J=7.1Hz,3H).

[0067] The preparation of compound (4) was carried out according to the literature (J. Agric. Food Chem. 2020, 68, 6347-6354), specifically by the following three methods:

[0068] Method 1: Add 15 mL of sodium hydroxide aqueous solution (6 mol / L) to compound (3) (5.41 g, 0.02 mol), stir and heat, and stir at 80 °C for 2 h. After the reaction solution is cooled, pour it into 60 mL of ice water, adjust the pH to 3-4 with concentrated hydrochloric acid, filter with a Buchner funnel, dry the filter cake, and obtain a white solid (4) (4.42 g; 91%). 1 H NMR (300MHz, DMSO) δ13.11(s,1H),7.51–7.34(m,5H),2.82–2.60(m,4H),1.89–1.64(m,4H).

[0069] Method 2: Add 15 mL of potassium hydroxide aqueous solution (6 mol / L) to compound (3) (5.41 g, 0.02 mol), stir and heat, and stir at 90 °C for 2 h. After the reaction solution is cooled, pour it into 60 mL of ice water, adjust the pH to 3-4 with concentrated hydrochloric acid, filter with a Buchner funnel, dry the filter cake, and obtain a white solid (4) (4.56 g; 94%).

[0070] Method 3: 15 mL of lithium hydroxide aqueous solution (6 mol / L) was added to compound (3) (5.41 g, 0.02 mol), stirred and heated, and stirred at 80 °C for 2 h. After the reaction solution was cooled, it was poured into 60 mL of ice water, and the pH was adjusted to 3-4 with concentrated hydrochloric acid. The mixture was filtered through a Buchner funnel, and the filter cake was dried to obtain a white solid (4) (4.27 g; 88%).

[0071] The preparation of compound (5) was carried out according to the literature (Eur.J.Med.Chem.2013,67,14-18). The specific steps are as follows: 15 mL of dichloromethane was added to compound (4) (4.36 g, 0.018 mol). At 0 °C, a solution of oxalyl chloride (3.43 g, 0.027 mol) in dichloromethane (10 mL) was slowly added dropwise. The mixture was stirred at room temperature for 4 h and concentrated to obtain compound (5). The synthesized compound (5) was directly used for the next step of the reaction.

[0072] The preparation of compound (6) was performed according to the literature (Eur. J. Med. Chem. 2013, 67, 14-18), and the specific steps were as follows: Glycine ethyl ester hydrochloride (3.77 g, 0.027 mol) was mixed with dry dichloromethane (60 mL), and triethylamine (2.73 g, 0.027 mol) was added. The resulting mixture was stirred at 0 °C for 10 minutes. Then, a dichloromethane (30 mL) solution of compound (5) (4.69 g, 0.018 mol) was slowly added dropwise to the mixture. The mixture was stirred at room temperature for 1 h, and after extraction and separation with dichloromethane, it was concentrated and purified by column chromatography to obtain a white solid (6) (4.42 g; 75%). 1 H NMR(500MHz,DMSO)δ8.87(t,J=6.0Hz,1H),7.47–7.39(m,4H),7.33–7.28(m,1H),4.15(q,J=7 .1Hz,2H),3.98(d,J=6.0Hz,2H),2.71–2.63(m,4H),1.82–1.69(m,4H),1.22(t,J=7.1Hz,3H).

[0073] Compound (7) was prepared according to the literature (Eur. J. Med. Chem. 2013, 67, 14-18), specifically by the following two methods:

[0074] Method 1: Compound (6) (4.42 g, 0.0135 mol) was added to 30 mL of methanol, followed by 5 mL of sodium hydroxide aqueous solution (6 mol / L). The mixture was stirred at room temperature for 6 h and then concentrated. The resulting mixture was diluted with 100 mL of water and acidified with 5% hydrochloric acid to pH 3, precipitating a solid. The solid was filtered and dried to give a white solid (7) (3.64 g; 90%). 1 H NMR (500MHz, DMSO) δ12.74(s,1H),8.81(t,J=6.0Hz,1H),7.50–7.27(m,5H),3.89(d,J=6.0Hz,2H),2.74–2.58(m,4H),1.85–1.67(m,4H).

[0075] Method 2: Compound (6) (4.42 g, 0.0135 mol) was added to 30 mL of methanol, followed by 5 mL of potassium hydroxide aqueous solution (6 mol / L). The mixture was stirred at room temperature for 6 h and then concentrated. The resulting mixture was diluted with 100 mL of water and acidified with 5% hydrochloric acid to pH 3, precipitating a solid. The solid was filtered and dried to give a white solid (7) (3.48 g; 86%).

[0076] The target compound I-09 was prepared by the following four methods:

[0077] Method 1: Compound (7) (0.50 g, 0.0016 mol), EDCI (0.37 g, 0.00192 mol), and DMAP (0.23 g, 0.00192 mol) were added to 20 mL of dichloromethane and stirred at room temperature for 1.5 h. Then, a mixture of 4-bromobenzylamine (0.36 g, 0.00192 mol) and dichloromethane (10 mL) was added dropwise. After the addition was complete, the mixture was stirred at room temperature overnight. The reaction solution was acid-washed, water-washed, dried, concentrated, and purified by column chromatography to obtain a white solid I-09 (0.41 g, 52%).

[0078] Method 2: Compound (7) (0.50 g, 0.0016 mol), EDCI (0.37 g, 0.00192 mol), and HOBt (0.26 g, 0.00192 mol) were added to 20 mL of dichloromethane and stirred at room temperature for 1.5 h. Then, a mixture of 4-bromobenzylamine (0.36 g, 0.00192 mol) and dichloromethane (10 mL) was added dropwise. After the addition was complete, the mixture was stirred at room temperature overnight. The reaction solution was acid-washed, water-washed, dried, concentrated, and purified by column chromatography to obtain a white solid I-09 (0.46 g, 58%).

[0079] Method 3: Compound (7) (0.50 g, 0.0016 mol), DIC (0.24 g, 0.00192 mol), and HOBt (0.26 g, 0.00192 mol) were added to 20 mL of dichloromethane and stirred at room temperature for 1.5 h. Then, a mixture of 4-bromobenzylamine (0.36 g, 0.00192 mol) in dichloromethane (10 mL) was added dropwise. After the addition was complete, the mixture was stirred at room temperature overnight. The reaction solution was acid-washed, water-washed, dried, concentrated, and purified by column chromatography to obtain a white solid I-09 (0.37 g, 48%).

[0080] Method 4: Compound (7) (0.50 g, 0.0016 mol), DCC (0.40 g, 0.00192 mol), and DMAP (0.23 g, 0.00192 mol) were added to 20 mL of dichloromethane and stirred at room temperature for 1.5 h. Then, a mixture of 4-bromobenzylamine (0.36 g, 0.00192 mol) in dichloromethane (10 mL) was added dropwise. After the addition was complete, the mixture was stirred at room temperature overnight. The reaction solution was filtered, acid-washed, water-washed, dried, concentrated, and purified by column chromatography to obtain a white solid I-09 (0.42 g, 54%).

[0081] By using the same method as described above to prepare compound I-09, only replacing R and n in formula I with the chain lengths and substituents shown in Table 1, compounds I-01 to I-22 can be obtained.

[0082] The appearance, melting point, and yield of some compounds of formula I are listed in Table 1. 1 The 1H NMR (hydrogen nuclear magnetic resonance) data are listed in Table 2.

[0083] Table 1 shows the melting point, appearance, and yield of some compounds in Formula I.

[0084]

[0085]

[0086] Table 2 shows the proton NMR spectra of some compounds in Formula I.

[0087]

[0088]

[0089] Example 2: Insecticidal activity of compound I against diamondback moth

[0090] Bioactivity was evaluated using the leaf-dipping method proposed by the International Committee on Resistance to Pesticides (IRAC). The specific steps were as follows: The target compound was dissolved in DMSO, and a certain amount of 0.05% (w / v) Triton X-100 buffer solution was added to prepare a 500 mg / L stock solution. The stock solution was continuously diluted with the buffer solution to different concentrations. Cabbage leaves were immersed in solutions with different pesticide concentrations for 3 seconds. Control leaves were treated with 0.05% Triton X-100 and DMSO solutions. After drying at room temperature for 2 hours, the leaves were placed in petri dishes (9 cm in diameter). Each concentration was repeated three times (15 second-instar larvae per repeat). Finally, the petri dishes were stored in an incubator at 25±2℃, 70±20% RH (relative humidity), and a 14:10h light:dark photoperiod. Results were checked after 72h, 96h, 120h, and 144h. The insects were considered dead if they could not crawl normally when gently touched with a needle. The formula for correcting the mortality rate is shown in Figure 1.

[0091] Corrected mortality rate (%) = (T – C) × 100 / (100% – C) (1)

[0092] Where T represents the mortality rate of the tested compound group, and C represents the mortality rate of the blank control group (T and C are expressed as percentages). If the mortality rate of the blank control is >20%, the experiment should be repeated. The insecticidal activity data of some compounds in Formula I against diamondback moth are shown in Table 3.

[0093] Table 3 shows the insecticidal activity (500 mg / L) of some compounds in Formula I against the diamondback moth.

[0094]

[0095] As shown in Table 3, some of the Formula I compounds provided by this invention exhibit moderate to good insecticidal activity against the tested diamondback moth. At a concentration of 500 mg / L, nine target compounds (I-01, I-03, I-04, I-06, I-07, I-09, I-10, I-15, and I-17) showed insecticidal activity exceeding 90%, and two compounds (I-09 and I-17) showed 100% insecticidal activity, demonstrating promising potential as insecticides for controlling the agricultural pest diamondback moth.

[0096] Example 3: Insecticidal activity of compound I against Asian corn borer

[0097] The bioactivity of a target compound against the Asian corn borer (Ostriniafurnacalis) was determined using a feed method (J. Agric. Food Chem. 2023, 71, 8345-8355). The specific steps were as follows: The target compound was dissolved in DMSO, and a certain amount of 0.05% (w / v) Triton X-100 buffer solution was added to prepare a 500 mg / L stock solution. The stock solution was continuously diluted with the buffer solution to different concentrations. Artificial feed was mixed with the test solution and placed in 9 cm petri dishes, with 15 second-instar larvae per group. Each concentration was repeated three times. Finally, the petri dishes were stored in an incubator at 25±2℃, 70% RH (relative humidity), and a 16:8h (light:dark photocycle). Results were examined after 96h, 120h, 144h, and 168h. The formula for correcting mortality was shown in Figure 1.

[0098] Corrected mortality rate (%) = (T – C) × 100 / (100% – C) (1)

[0099] The corrected mortality rate was assessed using formula (1), where T represents the mortality rate of the test compound group and C represents the mortality rate of the blank control group (T and C are expressed as percentages). Data on the insecticidal activity of some compounds in Formula I against the Asian corn borer are shown in Table 4.

[0100] Table 4 shows the insecticidal activity (500 mg / L) of some compounds in Formula I against the Asian corn borer.

[0101]

[0102] As shown in Table 4, some of the Formula I compounds provided by this invention exhibit good insecticidal activity against the tested Asian corn borer. At a concentration of 500 mg / L, 11 target compounds (I-01, I-02, I-03, I-05, I-06, I-07, I-08, I-09, I-12, I-15, and I-16) showed 100% insecticidal activity, demonstrating promise as insecticides for controlling the agricultural pest, the Asian corn borer.

[0103] Example 4: Insecticidal activity of compound I against fall armyworm.

[0104] The bioactivity of the tested pesticide against fall armyworm (Spodoptera frugiperda) was determined using the feed-film method. The target pesticide was dissolved in DMSO to prepare a 500 mg / L stock solution, which was continuously diluted to different concentrations with a buffer solution (0.05% (w / v) Triton X-100). The control group was prepared with equal volumes of DMSO and 0.05% (w / v) Triton X-100 solution. Artificial feed was added to 24-well culture plates. After the feed cooled and solidified, 100 μL of the pesticide solution was added to the surface of the feed. The plates were then allowed to dry at room temperature before inoculating each well with one second-instar larva. Each concentration was repeated three times (each time with 12 second-instar larvae). The 24-well culture plates were then stored in an incubator at 26°C, 85% RH (relative humidity), and a 16:8h (light:dark) photoperiod. Results were checked after 96 and 144 hours; the larvae were considered dead if they could not crawl normally when gently touched with a needle. The adjusted mortality rate is assessed using formula (1).

[0105] Corrected mortality rate (%) = (T – C) × 100 / (100% – C) (1)

[0106] The corrected mortality rate was assessed using formula (1), where T represents the mortality rate of the test compound group and C represents the mortality rate of the blank control group (T and C are expressed as percentages). Data on the insecticidal activity of some compounds in Formula I against fall armyworm are shown in Table 5.

[0107] Table 5 shows the insecticidal activity (500 mg / L) of some compounds in Formula I against the fall armyworm.

[0108]

[0109]

[0110] As shown in Table 5, some of the Formula I compounds provided by this invention exhibit certain insecticidal activity against the tested fall armyworm. At a concentration of 500 mg / L, some of the Formula I compounds show certain insecticidal activity against fall armyworm, with three compounds (I-09, I-15, and I-17) showing insecticidal activity of over 80% against fall armyworm, demonstrating promising potential as insecticides for controlling the agricultural pest fall armyworm.

[0111] Example 5: Activity test of compound I on the taproot growth of wild-type Arabidopsis thaliana in Colombia

[0112] Arabidopsis thaliana seeds were disinfected with 1% sodium hypochlorite solution for 15 min, rinsed with sterile water, and sown on 1 / 2 MS medium (0.8% agar, 1% sucrose, and a specified concentration of compound). After vernalization at 4℃ for 3 days, the seeds were transferred to an artificial climate chamber and cultured in light and dark conditions (16 / 8h, 22 / 19℃) for 7 days. Whole plants were photographed, and the length of the taproot was measured using ImageJ software. The taproot growth inhibition rate was calculated using the formula: Taproot growth inhibition rate (%) = (Taper root length of control group - Taproot length of drug group) / Taproot length of control group × 100%. The results are shown in Table 6.

[0113] Table 6 shows the inhibitory activity of some compounds in Formula I on the primary root growth of Arabidopsis thaliana (10). -4 M)

[0114]

[0115] As can be seen from Table 6, some of the compounds of Formula I provided in this invention have a good inhibitory effect on the main root of Arabidopsis thaliana. In 10 -4 At concentration M, the 10 target compounds (I-01, I-03, I-04, I-06, I-09, I-10, I-12, I-15, I-18 and I-19) exhibited more than 90% inhibitory activity against the taproot growth of Arabidopsis thaliana, showing promise for agricultural application as herbicides.

[0116] Example 6: Growth inhibitory activity test of compound I on ryegrass roots and stems.

[0117] Ryegrass (Lolium perenne L.) seeds were soaked in water for 24 hours. 10 mg of the compound was dissolved in 1 mL of DMSO, and then a 100 mg / L test solution was prepared using a 0.5% Tween 80 aqueous solution. Germination paper was placed in a 9 cm Petri dish, 5 mL of the test solution was added, and then 30 ryegrass seeds were evenly scattered on the dish. Each experiment was repeated three times. The mixture was sealed and incubated in a 25℃, 16h / 8h light / dark cycle incubator. Germination and growth of the weeds were observed daily. After 7 days of incubation, the root and stem lengths of 7-day-old seedlings were measured. The root (stem) growth inhibition rate was calculated using the formula: Root (stem) growth inhibition rate = (Root (stem) length of control group - Root (stem) length of drug group) / Root (stem) length of control group × 100%. The results are shown in Table 7.

[0118] Table 7 shows the growth-inhibiting activity (100 mg / L) of some compounds from Formula I on the roots and stems of ryegrass.

[0119]

[0120] As shown in Table 7, some of the Formula I compounds provided in this invention have a certain inhibitory effect on the roots and stems of ryegrass. At a concentration of 100 mg / L, six compounds (I-03, I-06, I-09, I-12, I-16, and I-22) showed an inhibition rate of over 60% on the root growth of ryegrass, and four compounds (I-03, I-06, I-09, and I-16) showed an inhibition rate of over 60% on the stem growth of ryegrass. I-09 showed the best activity, with an inhibition rate of over 70% on both roots and stems, demonstrating promising application as a herbicide for weed control in agriculture.

[0121] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. Compounds with the following general formula: n is 0 or 1; R1 represents a substituent on the benzene ring, which can be mono- or poly-substituted; R1 is independently selected from: H, halogen, C1-C6 alkyl, C1-C4 alkoxy, and halogenated C1-C4 alkyl.

2. The compound according to claim 1, characterized in that, R1 is independently selected from: H, fluorine, chlorine, bromine, methyl, methoxy, tert-butyl, and trifluoromethyl.

3. The compound according to claim 1 or 2, characterized in that, The compound is any one of the following: 。 4. A method for preparing the compound of claim 1, comprising the following steps: in an organic solvent, the compound of formula II and the compound of formula III undergo an amide condensation reaction to obtain the compound; In Equation III, n is 0 or 1; R1 represents a substituent on the benzene ring, which can be mono- or poly-substituted; R1 is independently selected from: H, halogen, C1-C6 alkyl, C1-C4 alkoxy, and halogenated C1-C4 alkyl.

5. The method according to claim 4, characterized in that, In the amidation reaction, a condensation reagent is added to activate the carboxyl group in the compound shown in Formula II; The condensing agent is at least one of DCC, DMAP, DIC, DIEA, EDCI, and HOBt. The temperature of the amide condensation reaction is 0~60℃, and the time is 1~24 hours; The molar ratio of the compound shown in Formula II to the compound shown in Formula III is 1:1 to 3.

6. The use of the compound according to any one of claims 1-3 in the control of agricultural pests and weeds.

7. The application according to claim 6, characterized in that, In this application, the pest is a lepidopteran pest; The weeds are either dicotyledonous or monocotyledonous.

8. The application according to claim 7, characterized in that, The pests include diamondback moth, Asian corn borer, and fall armyworm; the weeds include Arabidopsis thaliana and ryegrass.

9. An insecticide comprising or having said compound as an active ingredient, according to any one of claims 1-3.

10. A herbicide comprising or having said compound as an active ingredient, according to any one of claims 1-3.

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