Heterocyclic substituted N-pyridylbenzothiazole compounds and their preparation methods and applications

Abstract

The present invention belongs to the technical field of pesticides and discloses heterocyclic-substituted N-pyridylbenzothiazole compounds, their preparation methods, and applications. The present invention provides heterocyclic-substituted N-pyridylbenzothiazole compounds, which, at a low dose of 1.5 g / ha, have a control effect of ≥90% on a variety of weeds. Pre-emergence soil spraying of 4.5 to 9.0 g / ha or post-emergence stem and leaf spraying of 1.5 to 4.5 g / ha of heterocyclic-substituted N-pyridylbenzothiazole compounds exhibits good weed control effects on broadleaf weeds such as Amaranthus retroflexus, Abutilon, Chenopodium album, Portulaca oleracea, Veronica persica, and Geranium sibiricum, as well as grass weeds such as Echinochloa crus-galli and Setaria viridis. Spraying of 4.5 to 15 g / ha of heterocyclic-substituted N-pyridylbenzothiazole compounds has good crop safety for winter wheat, rice, and corn. The present invention provides an effective solution for the management of resistant weeds and offers a new approach to the development and creation of green chemical pesticides.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides and relates to a class of heterocyclic substituted N-pyridylbenzothiazole compounds and a preparation method and application thereof. Background Art

[0002] Weeds are a major cause of reduced crop yield and quality. Farmland weeds generally have a strong reproductive capacity. Their seeds are long-lived, tenacious, mature early, and shed easily, making them difficult to eradicate and possessing exceptional vitality. Weeds primarily compete with crops for nutrients, water, sunlight, and space, hindering field ventilation and light transmission, increasing the spread of pests and diseases, and thus reducing crop yield and quality. Some weeds also secrete inhibitory substances that hinder crop growth. Excessive weed growth can also affect the normal operation of water conservancy facilities, hinder agricultural operations, and increase production costs.

[0003] At present, weed control mainly controls weed growth by worsening the weed growth environment, such as: controlling weeds through agricultural control methods such as crop rotation, seed selection, reasonable close planting to control weeds, flooding to control weeds, etc.; controlling weeds through mechanical control methods such as deep plowing, harrowing, harrowing before seedlings, and tillage and weeding during the seedling stage; controlling weeds through biological control methods such as killing weeds with bacteria, insects, and plants; and controlling weeds through chemical weed control.

[0004] Chemical weed control is characterized by timely, rapid, and effective weed control. The main mechanisms of action of herbicides for weed control include inhibition of photosynthesis, inhibition of respiration, inhibition of nucleic acid and amino acid biosynthesis, inhibition of carotenoid biosynthesis, interference with plant hormones, inhibition of lipid synthesis, disruption of biofilms, and inhibition of plant growth. Currently available herbicides include triazines, amides, ureas, dinitroanilines, diphenyl ethers, phenoxycarboxylic acids, carbamates, and organophosphates.

[0005] However, existing herbicides have problems such as insufficient broad-spectrum weed control, poor weed control effect, easy occurrence of phytotoxicity, and high soil residues. At the same time, with the widespread use of herbicides, weeds are becoming increasingly resistant to existing chemical herbicides. Therefore, it is of great significance to develop herbicides with novel chemical structures and mechanisms of action. Summary of the Invention

[0006] To address the problems of existing herbicides, such as insufficient broad-spectrum weed control, poor weed control efficacy, phytotoxicity, and high soil residue, the present invention provides N-pyridylbenzothiazole compounds, their preparation methods, and applications. These heterocyclic-substituted N-pyridylbenzothiazole compounds exhibit good control efficacy against both broadleaf and grass weeds at an application rate of 1.5 to 9.0 g / ha and are crop-safe for common field crops such as winter wheat, rice, and corn.

[0007] To achieve the technical purpose of the present invention, on the one hand, the present invention provides an N-pyridylbenzothiazole compound, the chemical structure of which is shown in formula (I):

[0008]

[0009] In formula (I):

[0010] Q is a heterocycle;

[0011] R 1 Any one selected from H, F, Cl; preferably, R 1 is F;

[0012] R 2 Selected from any one of hydrogen and halogen; preferably, R 2 is Cl or F;

[0013] R 3 Any one selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, and NO2; preferably, R 3 It is any one of F, Cl, CF3, and NO2.

[0014] The heterocycle Q is selected from any one of Q1 to Q4, and the structural formulas of Q1 to Q4 are shown below:

[0015]

[0016] R in Q1 4 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl; preferably, R 4 It is CF3.

[0017] R in Q1 5 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C5 alkenyl, C3-C5 alkynyl; preferably, R 5 For CH3.

[0018] R in Q2 6Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, cyano C1-C4 alkyl; preferably, R 6 is CH3. R in Q2 7 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, cyano C1-C4 alkyl; preferably, R 7 is CH3. Y in Q2 is selected from any one of O and S; preferably, Y is S.

[0019] R in Q3 8 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 cyanoalkyl, C2-C5 alkenyl, C3-C5 alkynyl, C1-C4 haloalkyl, C2-C5 haloalkenyl, C3-C5 haloalkynyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl; preferably, R 8 CH3, CH2C≡CH.

[0020] R in Q4 9 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 cyanoalkyl, C2-C5 alkenyl, C3-C5 alkynyl, C1-C4 haloalkyl, C2-C5 haloalkenyl, C3-C5 haloalkynyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl; preferably, R 9 It is any one of CH3, CHF2, and CF3.

[0021] R in Q4 10 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C5 alkenyl, C3-C5 alkynyl; preferably, R 10 For CH3.

[0022] In another aspect, the present invention provides a method for preparing N-pyridylbenzothiazole compounds. The N-pyridylbenzothiazole compounds can be prepared from the intermediate compound III, and the synthesis route is as follows:

[0023]

[0024] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, R 1 、R 2 、R 3 R in N-pyridylbenzothiazole compounds 1 、R 2 、R 3 The same as R in the intermediate compound II-1 4 Compared with R in Q1 4The same, R in the intermediate compound II-3 10 Compared with R in Q4 10 same.

[0025] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, Preparation Route A is as follows: Intermediate Compound III is dissolved in a solvent, substituted (N,N-dimethylaminocarbonyl)aminocrotonate is added, and the mixture is heated to 30-150°C and stirred for 1-12 hours to obtain Compound II-1. The solvent is glacial acetic acid; the molar ratio of intermediate Compound III to (N,N-dimethylaminocarbonyl)aminocrotonate is 1.0:1.2. Preferably, the heating temperature is the reflux temperature of the solvent, and the stirring reaction time is 4 hours.

[0026] Compound II-1 is dissolved in a solvent, and an acid-binding agent and a halide are added to react to obtain compound I-1 of formula (I). The solvent is acetone, and the acid-binding agent is K2CO3. The molar ratio is compound II-1:halide:K2CO3 = 1.0:1.2:2. The reaction temperature is the reflux temperature of the solvent, and the reaction time is 4 hours.

[0027] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, Preparation Route B is as follows: Intermediate Compound III is dissolved in a solvent, an acid binder and carbonyldiimidazole (CDI) are added, the reaction is heated to 30-150°C, a substituted urea is added, and the reaction is stirred for 1-12 hours to obtain Compound I-2 of Formula (I). The solvent is ethyl acetate, and the acid binder is triethylamine; the molar ratio of intermediate Compound III: acid binder: CDI: urea is 1.0:1.2:2.0:1.2. Preferably, the heating temperature is the reflux temperature of the solvent, and the stirring reaction time is 2 hours.

[0028] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, Preparation Route C is as follows: Intermediate Compound III is dissolved in a solvent, methyl hydrazinecarboxylate, triethyl orthoformate, and a catalytic amount of acid are added, the mixture is heated to 30-150°C, an alkali metal salt is added, and the reaction is stirred for 1-12 hours to obtain Compound II-2. The solvent is methanol, the acid is p-toluenesulfonic acid, and the alkali metal salt is sodium methoxide; the molar ratio of intermediate Compound III: methyl hydrazinecarboxylate: triethyl orthoformate: p-toluenesulfonic acid: sodium methoxide is 1.0:1.1:1.1:0.02:1.4. Preferably, the heating temperature is 50-60°C, and the stirring reaction time is 4 hours.

[0029] Compound II-2 is dissolved in a solvent, and an acid-binding agent and a halide are added to react to yield compound I-3 of formula (I). The solvent is acetone, and the acid-binding agent is K2CO3. The molar ratio of compound II-2: halide: K2CO3 is 1.0:1.2:2.0. The reaction is carried out at the reflux temperature of the solvent for 4 hours.

[0030] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, preparation route D is: the intermediate compound III is diazotized and reduced to obtain hydrazine; hydrazine is added to aqueous ethanol with an equimolar aldehyde solution, stirred at room temperature for 4 hours, then an equimolar sodium cyanate is added and stirred at room temperature for 4 hours, and then treated with a 6% sodium hypochlorite aqueous solution with a volume twice that of the aldehyde solution, and stirred at room temperature for 12 hours to obtain compound II-3.

[0031] Compound II-3 is dissolved in a solvent, and an acid-binding agent and a halide are added to react to obtain compound I-4 of formula (I). The solvent is acetone, and the acid-binding agent is K2CO3. The molar ratio of compound II-3: halide: K2CO3 is 1.0:1.2:2.0. The reaction is carried out at the reflux temperature of the solvent for 4 hours.

[0032] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, the synthesis route of the intermediate compound III is as follows:

[0033]

[0034] Furthermore, in the method for preparing N-pyridylbenzothiazole compounds provided by the present invention, the raw material (X) is dissolved in a solvent, potassium ethylsulfonate is added, and the mixture is heated to 30-150°C and stirred for 1-24 hours to obtain the intermediate compound IX. The solvent is N,N-dimethylformamide (DMF); the molar ratio of raw material (X) to potassium ethylsulfonate is 1.0:2.0. Preferably, the heating temperature is 95°C, and the stirring reaction time is 4.0 hours.

[0035] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, SO₂Cl₂ is added to the intermediate compound IX, and the reaction is stirred at room temperature for 2.0 hours to obtain compound VIII. Compound VIII is dissolved in a solvent and heated to react for 12 hours to obtain compound VII. The solvent is concentrated hydrochloric acid:ethanol (1:1), and the heating reaction temperature is the solvent reflux temperature.

[0036] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, compound VII is dissolved in a solvent, 2-halopyridine (VI) and an acid-binding agent are added, and the mixture is heated to 30-150°C and stirred for 1-24 hours to obtain compound V. The solvent is N,N-dimethylformamide (DMF), and the acid-binding agent is K2CO3; the molar ratio of compound VII:2-halopyridine:acid-binding agent is 1.0:1.2:2.0. Preferably, the heating temperature is 120°C, and the stirring reaction time is 12 hours. The substituent X in the 2-halopyridine (VI) is a leaving group and is any one of fluorine, chlorine, bromine, iodine, p-toluenesulfonyl, and methylsulfonyl.

[0037] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, compound V is dissolved in a solvent, concentrated sulfuric acid is added, and the mixture is cooled to -10°C. A mixed solution of concentrated sulfuric acid and nitric acid is slowly added dropwise, and a nitration reaction is carried out for 10 to 30 minutes to obtain compound IV. The solvent is chloroform or dichloromethane, and the mixed solution is concentrated sulfuric acid: 68% nitric acid = 1.0:1.0.

[0038] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, Compound IV is dissolved in a solvent, reduced iron powder is added, and the mixture is heated to 30°C to 120°C and stirred for 1 to 12 hours to obtain the intermediate Compound III. The solvent is a 5% glacial acetic acid aqueous solution; the molar ratio of Compound IV to reduced iron powder is 1.0:5.0. Preferably, the heating temperature is 60°C to 80°C, and the stirring reaction time is 3 hours.

[0039] In another aspect, the present invention claims the use of N-pyridylbenzothiazole compounds for weed control, for controlling broadleaf weeds and / or grass weeds. Broadleaf weeds include Amaranthus retroflexus, Abutilon, Chenopodium album, Purslane, Veronica officinalis, and Geranium sibiricum; grass weeds include Echinochloa crus-galli and Setaria viridis.

[0040] In another aspect, the present invention claims protection for a herbicide comprising an N-pyridylbenzothiazole compound as an active ingredient. The formulation type of the herbicide is not specifically limited, and those skilled in the art may select from commonly used formulation types such as emulsifiable concentrates, suspension concentrates, dispersible oil suspensions, and wettable powders.

[0041] Furthermore, the present invention claims protection for a herbicidal composition comprising an N-pyridylbenzothiazole compound. The formulation type of the herbicidal composition is not particularly limited, and those skilled in the art may select from commonly used formulation types such as emulsifiable concentrates, suspension concentrates, dispersible oil suspensions, and wettable powders.

[0042] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0043] The heterocyclic-substituted N-pyridylbenzothiazole compound provided by the present invention has good herbicidal activity. When applied at a low dose of 1.5 g / ha, the control efficiency against various weeds is ≥90%. The present invention has shown through experiments that spraying 4.5 to 9.0 g / ha of the heterocyclic-substituted N-pyridylbenzothiazole compound on the soil before seedling emergence shows good herbicidal effect on broadleaf weeds such as Amaranthus retroflexus, Abutilon, Chenopodium album, Purslane, Veronica, and Geranium, as well as grass weeds such as Echinochloa crus-galli and Setaria viridis. Spraying 1.5 to 4.5 g / ha of the heterocyclic-substituted N-pyridylbenzothiazole compound on the stems and leaves after seedling emergence shows good herbicidal effect on broadleaf weeds such as Amaranthus retroflexus, Abutilon, Chenopodium album, Purslane, Veronica, and Geranium, as well as grass weeds such as Echinochloa crus-galli and Setaria viridis. The heterocyclic-substituted N-pyridylbenzothiazole compounds or salts thereof provided by the present invention are used for controlling weeds in field crop-growing areas and non-cultivated areas, have the characteristics of rapid action and high herbicidal activity, and can be used to control weeds that are resistant to existing herbicides, providing a new approach for the development and creation of green chemical pesticides.

[0044] The heterocyclic-substituted N-pyridylbenzothiazole compounds provided by the present invention have good crop safety, especially for common field crops such as winter wheat, rice, and corn. Experiments have demonstrated that pre-emergence soil spraying or post-emergence stem and foliage spraying of 4.5-15 g / ha of heterocyclic-substituted N-pyridylbenzothiazole compounds has no significant effect on the growth of winter wheat, rice, and corn, demonstrating good crop safety. This invention provides an effective solution for controlling resistant weeds. DETAILED DESCRIPTION

[0045] The technical solutions of the present invention are described below with reference to the following examples. However, the present invention is not limited to the following examples. The experimental methods and detection methods described in each example are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0046] Based on the preparation method of Compound I provided by the present invention, one of ordinary skill in the art can synthesize a series of heterocyclic-substituted N-pyridylbenzothiazole derivatives. Table 1 shows the specific structures of the substituent groups of the heterocyclic-substituted N-pyridylbenzothiazole derivatives.

[0047]

[0048] Table 1: R in N-pyridylbenzothiazole derivatives with different heterocyclic substitutions 1 、R 2 、R 3 and the group types of Q

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] Example 1

[0056] This example provides the preparation of the intermediate compound 5-amino-3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluorobenzothiazol-2(3H)-one (III-1).

[0057] 1. Preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-benzothiazol-2(3H)-one (V-1)

[0058] To a 100 mL reaction flask, 276 mg (2.0 mmol) of anhydrous KCO, 5.0 mL of dry N,N-dimethylformamide (DMF) solution, and 169 mg (1.0 mmol) of 6-fluorobenzothiazol-2(3H)-one (VII-1, prepared according to J. Heterocyclic Chem., 42, 727, 2005; CN201510559286.1) were added sequentially. After stirring in an 80°C oil bath for 30 min, 238 mg (1.1 mmol) of 2,3-dichloro-5-trifluoromethylpyridine (VI-1) was added and stirred in an oil bath at 110°C for 12 h. The reaction mixture was cooled, the pH adjusted to 2-3 with 1.0 M hydrochloric acid, and extracted with ethyl acetate (3 × 20 mL). The organic layer was washed with brine (3 × 20 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude sample. The crude sample was recrystallized from ethanol to obtain 293 mg of the product 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-benzothiazol-2(3H)-one (V-1), with a yield of 84.3%.

[0059] The H NMR spectrum of compound V-1 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.74 (d, 1.6Hz, 1H), 8.00 (d, J = 1.6Hz, 1H), 7.56 (dd, J = 6.8, 4.0Hz, 1H), 6.51 (dd, J = 6.4, 1.6Hz, 1H), 7.11 (td, J = 6.4, 1.6Hz, 1H).

[0060] The high resolution mass spectrum (HRMS) of compound V-1 is: C 13 H6ClF4N2OS[M+H]+, calculated value 348.9825, found value 348.9830.

[0061] The synthetic route of compound V-1 is as follows:

[0062]

[0063] 2. Preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-nitrobenzothiazol-2(3H)-one (IV-1)

[0064] In a 100 mL three-necked flask, 348 mg (1.0 mmol) of compound V-1 and 2 mL of dry dichloromethane solution were added in sequence. After the sample was dissolved, 2 mL of concentrated sulfuric acid was added, and the mixture was cooled to -10°C. 0.2 mL of a mixed solution of concentrated sulfuric acid / 68% nitric acid (1:1) was slowly added dropwise. After stirring in an ice bath for 30 minutes, the reaction solution was poured into ice water and continued to stir for 10 minutes. After filtration and drying, 389 mg of the final product, 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-nitrobenzothiazol-2(3H)-one (IV-1), was obtained in a yield of 99%.

[0065] The H NMR spectrum of compound IV-1 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.73 (d, J = 1.6 Hz, 1H), 8.54 (d, J = 4.0 Hz, 1H), 8.00 (d, J = 1.6 Hz, 1H), 7.69 (d, J = 6.4 Hz, 1H).

[0066] The high resolution mass spectrum (HRMS) of compound IV-1 is: C 13 H5ClF4N3O3S[M+H] + , calculated value 393.9676, measured value 393.9671.

[0067] The synthetic route of compound IV-1 is as follows:

[0068]

[0069] 3. Preparation of the intermediate compound 5-amino-3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluorobenzothiazol-2(3H)-one (III-1)

[0070] 280 mg of iron powder (5.0 mmol) was added to a 5% aqueous acetic acid solution (1.5 mL). The suspension was heated to 80°C, and then 393 mg (1.0 mmol) of compound IV-1 dissolved in 1.0 mL of acetic acid / ethyl acetate solution (1 / 1) was added. The mixture was then refluxed and stirred at 80°C for 3 h. After cooling, water and ethyl acetate (1 / 1) were added to the resulting mixture, and then filtered. The filtrate was extracted with ethyl acetate, and the organic phase was washed with water and sodium bicarbonate solution, dried, and concentrated to give 345 mg of the final product, 5-amino-3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluorobenzothiazol-2(3H)-one (III-1), in a yield of 95%. The product was directly carried out to the next step without purification.

[0071] The H NMR spectrum of compound III-1 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.74 (d, J = 1.6 Hz, 1H), 8.51 (d, J = 4.0 Hz, 1H), 8.00 (d, J = 1.6 Hz, 1H), 7.70 (d, J = 6.4 Hz, 1H), 4.52 (br, 2H).

[0072] The high resolution mass spectrum (HRMS) of compound III-1 is: C 13 H7ClF4N3OS[M+H] + , calculated value 363.99934, measured value 363.9939.

[0073] The synthetic route of intermediate compound III-1 is as follows:

[0074]

[0075] Example 2

[0076] This example provides the preparation of compound 3-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-1-methyl-6-(trifluoromethyl)-pyrimidine-2,4(1H,3H)-dione (No. 01).

[0077] To a 100 mL reaction flask, 363 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, and 305 mg (1.2 mmol) of ethyl (N,N-dimethylaminocarbonyl)amino 4,4,4-trifluoromethylbutenoate were added sequentially and heated under reflux with stirring for 4.0 h. The reaction mixture was cooled, diluted with water, and extracted with ethyl acetate (3 × 20 mL). The organic layer was washed with saturated sodium bicarbonate (3 × 20 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain intermediate compound II-1-1. Intermediate compound II-1-1 was dissolved in 20 mL of acetone, and 276 mg (2.0 mmol) of anhydrous K2CO3 and 170 mg (1.2 mmol) of iodomethane were added. The mixture was refluxed at 70°C for 4.0 h. The reaction mixture was cooled, and acetone was removed under reduced pressure. 20 mL of water was added, and the mixture was extracted with ethyl acetate (3×20 mL). The organic layer was washed with 1 M hydrochloric acid (3×20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 384 mg of the target product, Compound No. 01, in a yield of 71.2%.

[0078] H NMR spectrum of compound No.01 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.71 (d, 1.6Hz, 1H), 8.24 (d, J = 4.4Hz, 1H), 8.00 (d, J = 1.6Hz, 1H), 7.74 (d, J = 6.4Hz, 1H), 6.37 (s, 1H), 3.37 (s, 3H).

[0079] The high resolution mass spectrum (HRMS) of compound No.01 is: C 19 H9ClF7N4O3S[M+H]+, calculated value 540.9972, found value: 540.9968.

[0080] The synthetic route of compound No.01 is as follows:

[0081]

[0082] Example 3

[0083] This example provides the preparation of compound 3-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-3,5-dimethyl-6-thioxo-1,3,5-triazine-2,4-dione (No. 05).

[0084] To a 100 mL reaction flask, 363 mg (1.0 mmol) of intermediate compound III-1, 20.0 mL of dry ethyl acetate, 120 mg (1.2 mmol) of triethylamine, and 324 mg (2.0 mmol) of carbonyldiimidazole (CDI) were added sequentially. The mixture was heated to 50°C and reacted for 30 min. Subsequently, 125 mg (1.2 mmol) of N,N'-dimethylthiourea was added, and the mixture was heated to reflux and stirred for 2.0 h. The reaction mixture was cooled, washed with saturated brine (3 × 20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 308 mg of the target product, Compound No. 05, in a yield of 59.4%.

[0085] H NMR spectrum of compound No.05 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.73 (d, 1.6Hz, 1H), 8.02 (d, J = 4.0Hz, 1H), 7.99 (d, J = 1.6Hz, 1H), 7.73 (d, J = 6.4Hz, 1H), 3.67 (s, 6H).

[0086] The high resolution mass spectrum (HRMS) of compound No.05 is: C 18 H 11 ClF4N5O3S2[M+H]+, calculated value 519.9928, found value 519.9934.

[0087] The synthetic route of compound No.05 is as follows:

[0088]

[0089] Example 4

[0090] This example provides the preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-(5-oxo-1-(propargyl)-1H-1,2,4-triazol-4(5H)-yl)-benzothiazol-2(3H)-one (No. 09).

[0091] To a 100 mL reaction flask, 363 mg (1.0 mmol) of intermediate compound III-1, 100 mg (1.1 mmol) of methyl hydrazinecarboxylate, 165 mg (1.1 mmol) of triethyl orthoformate, 3.4 mg (0.02 mmol) of p-toluenesulfonic acid, and 10.0 mL of methanol were added sequentially and stirred at 50-60°C for 2.0 h. Subsequently, 10 mL of a methanol solution containing 76 mg (1.4 mmol) of sodium methoxide was added and stirring continued for 4.0 h. The reaction mixture was cooled, the methanol removed under reduced pressure, and 50 mL of water was added. The pH was adjusted to 1.0 with 1 M hydrochloric acid, and the mixture was filtered and dried to obtain intermediate compound II-2-1. Intermediate compound II-2-1 was dissolved in 20 mL of acetone, and 276 mg (2.0 mmol) of anhydrous K2CO3 and 143 mg (1.2 mmol) of propargyl bromide were added. The mixture was refluxed at 70°C for 4.0 h. The reaction mixture was cooled, and acetone was removed under reduced pressure. 20 mL of water was added, and the mixture was extracted with ethyl acetate (3×20 mL). The organic layer was washed with 1 M hydrochloric acid (3×20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 367 mg of the target product, Compound No. 09, in a yield of 78.3%.

[0092] H NMR spectrum of compound No.09 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.74 (d, 1.6Hz, 1H), 8.70 (s, 1H), 8.24 (d, J = 4.0Hz ,1H),7.99(d,J=1.6Hz,1H),7.70(d,J=6.4Hz,1H),4.85(s,2H),2.35(s,1H).

[0093] The high resolution mass spectrum (HRMS) of compound No.09 is: C 18 H9ClF4N5O2S[M+H]+, calculated value 470.0102, found value 470.0110.

[0094] The synthetic route of compound No.09 is as follows:

[0095]

[0096] Example 5

[0097] This example provides the preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-5-(3,4-dimethyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-6-fluoro-benzothiazol-2(3H)-one (No. 10).

[0098] To a 100 mL reaction flask, 363 mg (1.0 mmol) of intermediate compound III-1 and 5.0 mL of concentrated hydrochloric acid were added sequentially. After stirring at room temperature for 30 minutes, the mixture was cooled to 0°C and 1.0 mL of an aqueous solution containing 173 mg (2.5 mmol) of NaNO₂ was added dropwise. The mixture was stirred at 0°C for 3 hours. Subsequently, 1.0 mL of concentrated hydrochloric acid containing 852 mg of SnCl₂ (4.5 mmol) was added and stirring continued for 2 hours. The insoluble material was collected by filtration, dissolved in water, neutralized with 1 M sodium hydroxide, and extracted with ethyl acetate. The organic layer was washed with saturated sodium chloride aqueous solution (3 × 20 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain the intermediate compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-hydrazino-benzothiazol-2(3H)-one. The intermediate compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-hydrazino-benzothiazol-2(3H)-one was dissolved in 10 mL of 87% ethanol. 1.0 mL of an ethanol solution containing 45 mg (1.0 mmol) of acetaldehyde was slowly added dropwise below 10°C, followed by stirring at room temperature for 2 hours. Next, 2.0 mL of an aqueous solution containing 78 mg (1.2 mmol) of NaOCN was slowly added to the reaction flask, followed by 100 mg of glacial acetic acid. After complete addition, the mixture was stirred at room temperature for 4 hours. Next, 2.0 mL of a 6% aqueous NaClO solution was slowly added dropwise. After the addition was complete, the reaction mixture was stirred at room temperature for 12 hours. The mixture was poured into 50 mL of ice water to precipitate a solid, which was then filtered, washed with water, and dried to yield the intermediate compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-(3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl)-benzothiazol-2(3H)-one (II-3-1). The intermediate compound II-3-1 was dissolved in 20 mL of acetone, and 276 mg (2.0 mmol) of anhydrous K2CO3 and 170 mg (1.2 mmol) of iodomethane were added. The mixture was refluxed at 70°C for 4.0 h. The reaction mixture was cooled, the acetone removed under reduced pressure, and 20 mL of water was added. The mixture was extracted with ethyl acetate (3 × 20 mL). The organic layer was washed with 1 M hydrochloric acid (3 × 20 mL), dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography to yield 10223 mg of the target product, Compound No. 1, in a yield of 48.4%.

[0099] H NMR spectrum of compound No.08 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.73 (d, 1.6Hz, 1H), 8.30 (d, J = 4.0Hz, 1H), 7.99 (d, J = 1.6Hz, 1H), 7.61 (d, J = 6.8Hz, 1H), 3.31 (s, 3H), 2.25 (s, 3H).

[0100] The high resolution mass spectrum (HRMS) of compound No.08 is: C 17 H 11 ClF4N5O2S[M+H]+, calculated value 460.0258, found value: 460.0251.

[0101] The synthetic route of compound No.10 is as follows:

[0102]

[0103] Example 6

[0104] This example provides a type of processable formulation of heterocyclic substituted N-pyridylbenzothiazole compounds.

[0105] 1. Emulsion

[0106] Calculated by mass percentage, the composition comprises 10% of a heterocyclic substituted N-pyridylbenzothiazole compound, 5% of an AgrimerA1-101LC emulsifier, 37% of N-methyl-2-pyrrolidone, and soybean oil to make up to 100%.

[0107] 2. Suspension agent

[0108] Calculated by mass percentage, the composition includes 15% of heterocyclic substituted N-pyridylbenzothiazole compound, 3% of ethylene glycol, 5% of nonylphenol polyoxyethylene ether, 10% of sodium lignin sulfonate, 1% of sodium carboxymethyl cellulose, 1% of magnesium aluminum silicate, 0.8% of 75% silicone oil water emulsion, and water to make up to 100%.

[0109] 3. Dispersible oil suspension

[0110] Calculated by mass percentage, the composition includes 15% of a heterocyclic substituted N-pyridylbenzothiazole compound, 12% of Rhodia V0 / 02N, 3% of organic bentonite, 1% of fumed silica, 2% of citric acid, and methyl oleate to make up to 100%.

[0111] 4. Wettable powder

[0112] Calculated by mass percentage, the mixture comprises 15% of heterocyclic substituted N-pyridylbenzothiazole compound, 3% of sodium lauryl sulfate, 3% of sodium lignin sulfonate, 5% of naphthalenesulfonic acid formaldehyde condensate and light calcium carbonate to make up 100%.

[0113] Example 7

[0114] This example provides the herbicidal activity of heterocyclic substituted N-pyridylbenzothiazole compounds.

[0115] Refer to the visual inspection method in NY / T 1155.3-2006 and NY / T 1155.4-2006. Evaluate the herbicidal activity of the agent on a scale of 1 to 9 based on the symptoms and severity of damage to the test weeds. See Table 2 for the tested weed species.

[0116] Level 1: All dead;

[0117] Level 2: Equivalent to 0-2.5% of weeds in the blank control area;

[0118] Level 3: Equivalent to 2.6-5% of the weeds in the blank control area;

[0119] Level 4: Equivalent to 5.1-10% of the weeds in the blank control area;

[0120] Level 5: Equivalent to 10.1-15% of the weeds in the blank control area;

[0121] Level 6: Equivalent to 15.1-25% of the weeds in the blank control area;

[0122] Level 7: Equivalent to 25.1-35% of the weeds in the blank control area;

[0123] Level 8: Equivalent to 35.1-67.5% of the weeds in the blank control area;

[0124] Level 9: Equivalent to 67.6% to 100% of the weeds in the blank control area.

[0125] Table 2: Weed species tested

[0126]

[0127]

[0128] 1. Pre-emergence herbicidal activity of heterocyclic substituted N-pyridylbenzothiazole compounds

[0129] The pre-emergence herbicidal activity of heterocyclic-substituted N-pyridylbenzothiazole compounds was evaluated according to the method described in NY / T 1155.3-2006. Each heterocyclic-substituted N-pyridylbenzothiazole compound was prepared as a 10% emulsifiable concentrate according to the formulation described in Example 6. Soil spraying was performed one day after weed sowing, and herbicidal activity was assessed 21 days after treatment. The results are shown in Table 3.

[0130] Table 3: Pre-emergence herbicidal activity of heterocyclic substituted N-pyridylbenzothiazole compounds

[0131]

[0132]

[0133] As shown in Table 3, at application rates of 4.5 to 9.0 g / ha, the tested heterocyclic-substituted N-pyridylbenzothiazole compounds exhibited good pre-emergence weed control against Amaranthus retroflexus, Abutilon, Chenopodium album, Portulaca oleracea, Veronica officinalis, Geranium sibiricum, Echinochloa crus-galli, and Setaria viridis. This indicates that the heterocyclic-substituted N-pyridylbenzothiazole compounds prepared by the present invention can effectively control grass and broadleaf weeds at low pre-emergence application rates.

[0134] 2. Post-emergence herbicidal activity of heterocyclic substituted N-pyridylbenzothiazole compounds

[0135] The postemergence herbicidal activity of heterocyclic-substituted N-pyridylbenzothiazoles was evaluated according to the method described in NY / T 1155.4-2006. Each heterocyclic-substituted N-pyridylbenzothiazole was formulated into a 10% emulsifiable concentrate according to the formulation described in Example 6. Foliar spraying was performed on grass weeds at the 2- to 3-leaf stage and broadleaf weeds at the 3- to 4-leaf stage. The results of the investigation 21 days after treatment are shown in Table 4.

[0136] Table 4: Post-emergence herbicidal activity of heterocyclic substituted N-pyridylbenzothiazole compounds

[0137]

[0138]

[0139] As shown in Table 4, at application rates of 1.5 to 4.5 g / ha, the tested heterocyclic-substituted N-pyridylbenzothiazole compounds exhibited good post-emergence weed control against Amaranthus retroflexus, Abutilon, Chenopodium album, Portulaca oleracea, Veronica officinalis, Geranium sibiricum, Echinochloa crus-galli, and Setaria viridis. This indicates that the heterocyclic-substituted N-pyridylbenzothiazole compounds prepared by the present invention can effectively control grass and broadleaf weeds at low post-emergence application rates.

[0140] Example 8

[0141] This example provides a safety evaluation test of heterocyclic-substituted N-pyridylbenzothiazole compounds on crops.

[0142] The phytotoxicity evaluation of the heterocyclic substituted N-pyridylbenzothiazole compounds was carried out according to the method in NY / T1965.2-2010. The evaluation was based on the fresh weight growth inhibition rate of the test crops. The specific indicators were:

[0143] Inhibition rate is 0: safe, no phytotoxicity;

[0144] Inhibition rate is 1% to 10%: slight phytotoxicity;

[0145] Inhibition rate is 11% to 30%: moderate phytotoxicity;

[0146] Inhibition rate is 31% to 50%: severe phytotoxicity;

[0147] Inhibition rate > 50%: severe phytotoxicity.

[0148] Crop safety evaluations were conducted using winter wheat, rice, corn, and soybeans according to the method outlined in NY / T 1965.2-2010. The heterocyclic-substituted N-pyridylbenzothiazole compound was formulated as a 10% emulsifiable concentrate according to the formulation described in Example 6 and applied at three doses: 4.5 g / ha, 9.0 g / ha, and 15 g / ha. The results of the crop safety evaluations are shown in Table 5.

[0149] Table 5: Safety evaluation results of heterocyclic substituted N-pyridylbenzothiazole compounds

[0150]

[0151] As shown in Table 5, at a dosage of 4.5 to 15 g / ha, soil and foliar application of compounds No. 01 and No. 13 had no significant effect on the growth of winter wheat, rice, and corn. However, at a high dosage (15 g / ha), the test compounds had a slight inhibitory effect on soybeans. This indicates that the heterocyclic-substituted N-pyridylbenzothiazole compounds prepared in this invention have good crop safety for the common field crops of winter wheat, rice, and corn.

[0152] The embodiments described above are some of the embodiments of the present invention, rather than all of them. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but rather merely represents selected embodiments of the present invention. All other embodiments obtained without creative effort and through deduction and substitution by a person of ordinary skill in the art based on the concept of the present invention are within the scope of protection of the present invention.

Claims

1. A heterocyclic substituted N -pyridylbenzothiazole compounds, characterized in that The chemical structure is shown in formula (I): ； In formula (I): Q is a heterocycle; R 1 is F; R 2 is Cl or F; R 3 Any one of F, Cl, CF3, and NO2; The heterocycle Q is ; The R in Q1 4 CF3, R 5 For CH3.

2. The heterocyclic substituted N -A method for preparing a pyridylbenzothiazole compound, characterized in that: Using intermediate compound III as the synthetic raw material, synthetic route A was adopted: ； Compound R 5 The X group in -X is a halogen.

3. The preparation method according to claim 2, characterized in that In the intermediate compound III, R 1 F; R 2 is Cl or F; R 3 Any one of F, Cl, CF3, and NO2; The synthetic route of the intermediate compound III is as follows: The substituent X of compound VI is a leaving group, and the leaving group is any one of fluorine, chlorine, bromine, iodine, p-toluenesulfonyl, and methylsulfonyl.

4. The heterocyclic substituted N -Application of pyridylbenzothiazole compounds in weed control.

5. The use according to claim 4, characterized in that described N -Pyridylbenzothiazole compounds are used to control broadleaf weeds and / or grass weeds.

6. A herbicide, characterized in that The active ingredient of the herbicide comprises the herbicide according to claim 1 N -Pyridylbenzothiazole compounds.

7. A herbicidal composition, characterized in that The herbicidal composition comprises the herbicide according to claim 1 N -Pyridylbenzothiazole compounds.

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