N-pyridylbenzothiazole compounds and their preparation methods and applications

Abstract

The present invention belongs to the field of pesticide technology and discloses N-pyridylbenzothiazole compounds and their preparation methods and applications. Spraying 4.5 to 9.0 g / ha of the N-pyridylbenzothiazole compounds on the soil before seedling emergence or spraying 1.5 to 4.5 g / ha of the N-pyridylbenzothiazole compounds on the stems and leaves after seedling emergence shows good control effects on broad-leaved 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. Crop safety tests show that the N-pyridylbenzothiazole compounds are safe for winter wheat, rice, and corn at an application rate of 4.5 to 15.0 g / ha. The present invention provides an effective solution for the management of resistant weeds and can develop the N-pyridylbenzothiazole compounds into herbicides with broad market prospects.

Description

Technical Field

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

[0002] Weeds are a major factor in reducing crop yields. They compete with crops for nutrients, water, sunlight, and space, hindering field ventilation and light penetration, thereby reducing crop yield and quality. Some weeds can also secrete harmful substances that irritate plants and affect their growth.

[0003] The main methods of weed control include physical weeding, biological weeding, mechanical weeding, and chemical weeding. Physical weeding involves weeding using methods such as mulching, shading, and high temperatures. Biological weeding involves the use of animals, insects, and pathogens to control certain weeds. Mechanical weeding involves plowing, harrowing, and loosening the soil before sowing, before seedling emergence, and during various growth stages. Chemical weed control utilizes chemical herbicides, which are highly effective, labor-saving, and can eliminate the need for weeding in the field. Currently, commercially available herbicides are classified into nearly 20 categories based on their chemical structure. The main herbicides include triazines, amides, ureas, dinitroanilines, diphenyl ethers, phenoxycarboxylic acids, carbamates, and organophosphates.

[0004] 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

[0005] 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 an N-pyridylbenzothiazole compound. The N-pyridylbenzothiazole compound is substituted with a cyclic imino group and exhibits good control efficacy against both broadleaf and grass weeds at an application rate of 1.5 to 9.0 g / ha. It is also crop-safe for common field crops such as winter wheat, rice, and corn.

[0006] 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):

[0007]

[0008] In formula (I):

[0009] Q is a cyclic imino group;

[0010] X is selected from any one of halogen, CH3, CF3, and CN; preferably, X is F.

[0011] R 1 Any one selected from hydrogen and halogen elements; preferably, R 1 is Cl or F.

[0012] R 2 Any one selected from halogen elements, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, and NO2; preferably, R 2 It is any one of F, Cl, CF3, and NO2.

[0013] The cycloimino group Q is selected from any one of Q1 to Q14, and the structural formulas of Q1 to Q14 are shown below:

[0014]

[0015] R in Q6 3 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy; preferably, R in Q6 3 For CH3.

[0016] R in Q6 4 Any one selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy; preferably, R in Q6 4 For CH3.

[0017] R in Q13 5 Any one selected from hydrogen, hydroxyl, amino, nitro, thiol, carboxyl, carboxylate, halogen element, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy; preferably, R in Q13 5 For hydrogen.

[0018] R in Q14 7 are selected from any one of hydrogen, hydroxyl, amino, nitro, thiol, carboxyl, carboxylate, halogen element, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, and C1-C4 haloalkoxy; preferably, R in Q14 7 is hydrogen. R in Q13 5 and R in Q14 7 It is located at any substitution position of the aromatic ring, either monosubstituted or polysubstituted.

[0019] R in Q14 6Any one selected from hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C6 haloalkyl, C3-C6 haloalkenyl, C3-C6 haloalkynyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl; preferably, R in Q14 6 It is CH3 or CH2C≡CH.

[0020] 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:

[0021]

[0022] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, the intermediate compound III is dissolved in a solvent, anhydrides (IIa to IIo) and a reducing agent are added, and the mixture is heated to 30 to 150° C. and stirred for 1 to 12 hours to obtain the N-pyridylbenzothiazole compound. The solvent is glacial acetic acid, and the reducing agent is iron powder. The molar ratio of intermediate compound III: anhydride: iron powder is 1.0:1.2:10. Preferably, the heating temperature is the reflux temperature of the solvent, and the stirring reaction time is 4 hours.

[0023] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, X, R in the intermediate compound III 1 、R 2 and X, R in N-pyridylbenzothiazole compounds 1 、R 2 Same. R in the anhydride 3 、R 4 、R 5 、R 6 、R 7 R in the cycloimino group 3 、R 4 、R 5 、R 6 、R 7 same.

[0024] 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:

[0025]

[0026] Furthermore, in the method for preparing N-pyridylbenzothiazole compounds provided by the present invention, the raw material (XI) is dissolved in a solvent, followed by the addition of potassium ethylsulfonate, the mixture is heated to 30-150°C, and stirred for 1-24 hours to obtain the intermediate compound VIII. The solvent is N,N-dimethylformamide (DMF); the molar ratio of raw material (XI) to potassium ethylsulfonate is 1.0:2.0; preferably, the heating temperature is 95°C, and the stirring reaction time is 4.0 hours.

[0027] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, sulfonyl chloride (SO2Cl2) is added to the intermediate compound VIII, and the reaction is stirred at room temperature for 2.0 h to obtain compound VII.

[0028] Furthermore, in the method for preparing N-pyridylbenzothiazole compounds provided by the present invention, compound VII is dissolved in a solvent and heated for 12 hours to obtain compound VI. The solvent is concentrated hydrochloric acid:ethanol (1:1), and the heating reaction temperature is the reflux temperature of the solvent.

[0029] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, compound VI is dissolved in a solvent, 2-halopyridine (V) 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 IV. The solvent is N,N-dimethylformamide (DMF), and the acid-binding agent is K2CO3; the molar ratio of compound VI: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 Z of the 2-halopyridine is a leaving group, and is any one of fluorine, chlorine, bromine, iodine, p-toluenesulfonyl, and methylsulfonyl.

[0030] Furthermore, in the preparation method of N-pyridylbenzothiazole compounds provided by the present invention, compound IV is dissolved in a solvent, concentrated sulfuric acid is added, the mixture is cooled to -10°C, and a mixed acid solution is slowly added dropwise. A nitration reaction is carried out for 10 to 30 minutes to obtain the intermediate compound III. The solvent is chloroform or dichloromethane; the mixed acid is concentrated sulfuric acid: 68% nitric acid in a ratio of 1.0:1.0.

[0031] In another aspect, the present invention claims the use of N-pyridylbenzothiazole compounds for weed control. The N-pyridylbenzothiazole compounds are used to control broadleaf weeds and / or grass weeds. Specifically, broadleaf weeds include Amaranthus retroflexus, Abutilon, Chenopodium album, Purslane, Veronica officinalis, and Geranium strychnifolium; grass weeds include Echinochloa crus-galli and Setaria viridis.

[0032] In another aspect, the present invention claims protection for a herbicide comprising the 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 commonly used formulation types such as emulsifiable concentrates, suspension concentrates, dispersible oil suspensions, and wettable powders.

[0033] Furthermore, the present invention claims protection for a herbicidal composition comprising the N-pyridylbenzothiazole compound. The formulation type of the herbicidal composition is not specifically limited, and those skilled in the art may select commonly used formulation types such as emulsifiable concentrates, suspension concentrates, dispersible oil suspensions, and wettable powders.

[0034] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0035] The N-pyridylbenzothiazole compound provided by the present invention is substituted with a cyclic imino group and has a good control effect on broadleaf weeds and grass weeds under low-dose conditions. The present invention has shown through experiments that spraying 4.5 to 9.0 g / ha of the cyclic imino-substituted N-pyridylbenzothiazole compound on the soil before seedling emergence shows a good weed control 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 cyclic imino-substituted N-pyridylbenzothiazole compound on the stems and leaves after seedling emergence shows a good weed control 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.

[0036] The 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 shown that spraying 4.5 to 15 g / ha of cycloimino-substituted N-pyridylbenzothiazole compounds on the soil before emergence or on the stems and leaves after emergence 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention.

[0038] Figure 1 This is the single crystal diffraction structure diagram of compound No.01. DETAILED DESCRIPTION

[0039] 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.

[0040] 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 cycloimino-substituted N-pyridylbenzothiazole derivatives. Table 1 shows the specific structures of the substituent groups of the cycloimino-substituted N-pyridylbenzothiazole derivatives.

[0041]

[0042] Table 1: R in N-pyridylbenzothiazole derivatives with different cyclic imino substitutions 1 、R 2 , X and Q group types

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] Example 1

[0051] This example provides the preparation of the intermediate compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-nitrobenzothiazol-2(3H)-one (III-1).

[0052] 1. Preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-benzothiazol-2(3H)-one (IV-1)

[0053] 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 (VI-1) were added sequentially (for the preparation of 6-fluorobenzothiazol-2(3H)-one, see J. Heterocyclic Chem., 42, 727, 2005, and CN201510559286.1). After stirring in an 80°C oil bath for 30 min, 238 mg (1.1 mmol) of 2,3-dichloro-5-trifluoromethylpyridine (V-1) was added and stirred in a 120°C oil bath 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 (IV-1), with a yield of 84.3%.

[0054] The H NMR spectrum of compound IV-1 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.74 (d, J = 1.6 Hz, 1H), 8.00 (d, J = 1.6 Hz, 1H), 7.56 (d d, J=6.8, 4.0Hz, 1H), 7.51 (dd, J=6.4, 1.6Hz, 1H), 7.11 (td, J=6.4, 1.6Hz, 1H).

[0055] The high resolution mass spectrum (HRMS) of compound IV-1 is: C 13 H6ClF4N2OS[M+H] + , calculated value 348.9825, measured value 348.9830.

[0056] The synthetic route of compound IV-1 is as follows:

[0057]

[0058] 2. Preparation of the intermediate compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-5-nitrobenzothiazol-2(3H)-one (III-1)

[0059] To a 100-mL three-necked flask, 348 mg (1.0 mmol) of compound IV-1 and 2 mL of dry dichloromethane solution were added. Once dissolved, 2 mL of concentrated sulfuric acid was added. The mixture was cooled to -10°C and slowly added dropwise with 0.2 mL of a 1:1 mixture of concentrated sulfuric acid and 68% nitric acid. After stirring on ice for 30 minutes, the reaction solution was poured into ice water and stirred for another 10 minutes. After filtration and drying, the final intermediate compound III-1 (389 mg) was obtained in a 99.0% yield. The product was directly processed into the next step without purification.

[0060] The H NMR spectrum of compound III-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).

[0061] The high resolution mass spectrum (HRMS) of compound III-1 is: C 13 H5ClF4N3O3S[M+H] + , calculated value 393.9676, measured value 393.9671.

[0062] The synthetic route of intermediate compound III-1 is as follows:

[0063]

[0064] Example 2

[0065] This example provides the preparation of compound 2-(3-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-4,5,6,7-tetrahydro-1H-isoindole-1,3(2H)-dione (No. 01).

[0066] In a 100 mL reaction flask, 393 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, 182 mg (1.2 mmol) of 3,4,5,6-tetrahydrophthalic anhydride (IIa) and 560 mg (10.0 mmol) of reduced iron powder were added in sequence 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 a crude sample. The crude sample was recrystallized from ethanol to obtain 443 mg of the final product, compound No.01, with a yield of 89.3%. The single crystal diffraction structure of compound No.01 is shown as follows Figure 1 shown.

[0067] H NMR spectrum of compound No.01 ( 1 H NMR) is: (400MHz, CDCl3) δ: 9.09 (d, J = 4.0Hz, 1H), 8.71 (d, J = 1.6Hz, 1H), 7.99 ( d,J=1.6Hz,1H),7.31(d,J=6.8Hz,1H),2.39-2.42(m,4H),1.75-1.78(m,4H).

[0068] The high resolution mass spectrum (HRMS) of compound No.01 is: C 21 H 13 ClF4N3O3S[M+H] + , calculated value 498.0302, measured value 498.0311.

[0069] The synthetic route of compound No.01 is as follows:

[0070]

[0071] Example 3

[0072] This example provides the preparation of compound 1-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-3,4-dimethyl-3-pyrroline-2,5(1H)-dione (No. 06).

[0073] To a 100 mL reaction flask, 393 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, 151 mg (1.2 mmol) of 3,4-dimethylfuran-2,5-dione (IIf-1), and 560 mg (10.0 mmol) of reduced iron powder 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 a crude sample. The crude sample was recrystallized from ethanol to obtain 410 mg of the final product, Compound No. 06, in an 87.1% yield.

[0074] H NMR spectrum of compound No.06 ( 1 H NMR) is: (400MHz, CDCl3) δ: 9.03 (d, J = 4.0 Hz, 1H), 8.74 (d, J = 1.6 Hz, 1H), 7.99 (d, J = 1.6 Hz, 1H), 7.78 (d, J = 6.4 Hz, 1H), 2.27 (s, 6H).

[0075] The high resolution mass spectrum (HRMS) of compound No.06 is: C19 H 11 ClF4N3O3S[M+H] + , calculated value 472.0146, measured value 472.0140.

[0076] The synthetic route of compound No.06 is as follows:

[0077]

[0078] Example 4

[0079] This example provides the preparation of compound 2-(3-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-3a,4,7,7a-tetrahydro-4,7-epoxy-1H-isoindole-1,3(2H)-dione (No. 09).

[0080] To a 100 mL reaction flask, 393 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, 199 mg (1.2 mmol) of 3a,4,7,7a-tetrahydro-4,7-epoxyisobenzofuran-1,3-dione (IIi), and 560 mg (10.0 mmol) of reduced iron powder 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 a crude sample. The crude sample was recrystallized from ethanol to obtain 414 mg of the final product, Compound No. 09, in an 81.3% yield.

[0081] H NMR spectrum of compound No.09 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.74 (d, J = 1.6 Hz, 1H), 8.17 (d, J = 4.0 Hz, 1H), 8.00 (d, J = 1.6H) z, 1H), 7.57 (d, J = 6.4Hz, 1H), 6.48-6.20 (m, 2H), 5.24-5.28 (m, 2H), 3.27-3.29 (m, 2H).

[0082] The high resolution mass spectrum (HRMS) of compound No.09 is: C 21 H 11 ClF4N3O4S[M+H] + , calculated value 512.0095, measured value 512.0101.

[0083] The synthetic route of compound No.09 is as follows:

[0084]

[0085] Example 5

[0086] This example provides the preparation of compound 2-(3-(3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)isoindole-1,3-dione (No. 13).

[0087] To a 100 mL reaction flask, 393 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, 177 mg (1.2 mmol) of phthalic anhydride (IIn-1), and 560 mg (10.0 mmol) of reduced iron powder 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 x 20 mL). The organic layer was washed with saturated sodium bicarbonate (3 x 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 the final product, Compound No. 13437 mg, in an 88.7% yield.

[0088] The H NMR spectrum of compound No.13 ( 1 H NMR) is: (400MHz, CDCl3) δ: 9.33 (d, J = 4.0Hz, 1H), 8.74 (d, J = 1.6Hz, 1H), 8.00 ( d,J=1.6Hz,1H),7.92-7.96(m,2H),7.78-7.80(m,2H),7.30(d,J=6.4Hz,1H).

[0089] The high resolution mass spectrum (HRMS) of compound No.13 is: C 21 H9ClF4N3O3S[M+H] + , calculated value 493.9989, measured value 493.9981.

[0090] The synthetic route of compound No.13 is as follows:

[0091]

[0092] Example 6

[0093] This example provides the preparation of compound 3-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)-6-fluoro-2-oxo-2,3-dihydrobenzothiazol-5-yl)-1-methylquinazoline-2,4(1H,3H)-dione (No. 14).

[0094] To a 100 mL reaction flask, 393 mg (1.0 mmol) of intermediate compound III-1, 5.0 mL of dry glacial acetic acid, 212 mg (1.2 mmol) of N-methylisatoic anhydride (IIo-1), and 560 mg (10.0 mmol) of reduced iron powder 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 x 20 mL). The organic layer was washed with saturated sodium bicarbonate (3 x 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 the final product, Compound No. 14446 mg, in a yield of 85.5%.

[0095] H NMR spectrum of compound No.14 ( 1 H NMR) is: (400MHz, CDCl3) δ: 8.73 (d, J=1.6Hz, 1H), 8.24 (d, J=4.0Hz, 1H), 8.00 (d, J= 1.6Hz,1H),7.92-7.96(m,1H),7.48-7.53(m,2H),7.24-7.28(m,2H),3.49(s,3H).

[0096] The high resolution mass spectrum (HRMS) of compound No.14 is: C 22 H 12 ClF4N4O3S[M+H] + , calculated value 523.0255, measured value 523.0260.

[0097] The synthetic route of compound No.14 is as follows:

[0098]

[0099] Example 7

[0100] This example provides a processable formulation type of cyclic imino-substituted N-pyridylbenzothiazole compounds.

[0101] 1. Emulsion

[0102] Calculated by mass percentage, the composition comprises 10% of a cyclic imino-substituted N-pyridylbenzothiazole compound, 5% of an AgrimerA1-101LC emulsifier, 37% of N-methyl-2-pyrrolidone, and soybean oil to make up to 100%.

[0103] 2. Suspension agent

[0104] Calculated by mass percentage, the composition includes 15% of a cyclic imino-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 a 75% silicone oil aqueous emulsion, and water to make up to 100%.

[0105] 3. Dispersible oil suspension

[0106] Calculated by mass percentage, the composition includes 15% of a cyclic imino-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%.

[0107] 4. Wettable powder

[0108] Calculated by mass percentage, the composition comprises 15% of a cyclic imino-substituted N-pyridylbenzothiazole compound, 3% of sodium lauryl sulfate, 3% of sodium lignin sulfonate, 5% of a naphthalenesulfonic acid formaldehyde condensate and light calcium carbonate to make up 100%.

[0109] Example 8

[0110] This example provides the herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds.

[0111] 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.

[0112] Level 1: All dead;

[0113] Level 2: Equivalent to 0-2.5% of weeds in the blank control area;

[0114] Level 3: Equivalent to 2.6-5% of the weeds in the blank control area;

[0115] Level 4: Equivalent to 5.1-10% of the weeds in the blank control area;

[0116] Level 5: Equivalent to 10.1-15% of the weeds in the blank control area;

[0117] Level 6: Equivalent to 15.1-25% of the weeds in the blank control area;

[0118] Level 7: Equivalent to 25.1-35% of the weeds in the blank control area;

[0119] Level 8: Equivalent to 35.1-67.5% of the weeds in the blank control area;

[0120] Level 9: Equivalent to 67.6% to 100% of the weeds in the blank control area.

[0121] Table 2: Weed species tested

[0122] Chinese name Latin name abbreviation Amaranthus retroflexus Amaranthus retroflexus AMA Ramie Abutilon theophrasti ABU quinoa Chenopodium album CHE purslane Portulaca oleracea POR Veronica Veronica polita VER wild geranium Geranium carolinianum GER barnyard grass Echinochloa crusgalli ECH Setaria Setaria viridis SET

[0123] 1. Pre-emergence herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds

[0124] The pre-emergence herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds was evaluated according to the method described in NY / T 1155.3-2006. Each cyclic imino-substituted N-pyridylbenzothiazole compound was prepared as a 10% emulsifiable concentrate according to the formulation shown in Example 7. 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.

[0125] Table 3: Pre-emergence herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds

[0126]

[0127]

[0128] As shown in Table 3, at application rates of 4.5 to 9.0 g / ha, the tested cyclic imino-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 cyclic imino-substituted N-pyridylbenzothiazole compounds prepared by the present invention can effectively control grass and broadleaf weeds at low pre-emergence application rates.

[0129] 2. Post-emergence herbicidal activity of cycloimino-substituted N-pyridylbenzothiazole compounds

[0130] The postemergence herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds was evaluated according to the method described in NY / T 1155.4-2006. Each cyclic imino-substituted N-pyridylbenzothiazole compound was prepared as a 10% emulsifiable concentrate according to the formulation shown in Example 7. 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.

[0131] Table 4: Post-emergence herbicidal activity of cyclic imino-substituted N-pyridylbenzothiazole compounds

[0132]

[0133]

[0134]

[0135] As shown in Table 4, at application rates of 1.5 to 4.5 g / ha, the tested cyclic imino-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 cyclic imino-substituted N-pyridylbenzothiazole compounds prepared by the present invention can effectively control grass and broadleaf weeds at low post-emergence application rates.

[0136] Example 9

[0137] This example provides a safety evaluation test of cyclic imino-substituted N-pyridylbenzothiazole compounds on crops.

[0138] The phytotoxicity evaluation of the tested cyclic imino-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 tested crops. The specific indicators were:

[0139] Inhibition rate is 0: safe, no phytotoxicity;

[0140] Inhibition rate is 1% to 10%: slight phytotoxicity;

[0141] Inhibition rate is 11% to 30%: moderate phytotoxicity;

[0142] Inhibition rate is 31% to 50%: severe phytotoxicity;

[0143] Inhibition rate > 50%: severe phytotoxicity.

[0144] Crop safety evaluations were conducted using winter wheat, rice, corn, and soybeans according to the method outlined in NY / T 1965.2-2010. The cyclic imino-substituted N-pyridylbenzothiazole compounds were formulated into 10% emulsifiable concentrates according to the formulation described in Example 7 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.

[0145] Table 5: Safety evaluation results of cyclic imino-substituted N-pyridylbenzothiazole compounds

[0146]

[0147]

[0148] As shown in Table 5, at a dosage of 4.5 to 15 g / ha, soil and foliar application of compounds No. 01, No. 06, No. 15, and No. 20 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 soybean. This indicates that the cycloimino-substituted N-pyridylbenzothiazole compounds prepared in this invention have good crop safety for the common field crops of winter wheat, rice, and corn.

[0149] 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 N -pyridylbenzothiazole compounds, whose chemical structure is shown in formula (I): ； In formula (I): Q is a cyclic imino group; X is F; R 1 is Cl or F; R 2 Any one of F, Cl, CF3, and NO2; The cyclic imino group Q is selected from Q1, Q6 、 Any of the following; The R in Q6 3 CH3, R 4 For CH3.

2. The method according to claim 1 N -A method for preparing a pyridylbenzothiazole compound, characterized in that: The intermediate compound III is reacted with anhydride to form the N -pyridylbenzothiazole compounds; The acid anhydride is selected from IIa, IIf 、 Any of the following; R in the acid anhydride IIf 3 is CH3; R in the acid anhydride IIf 4 is CH3; The chemical structure of the intermediate compound III is shown in formula (III): ； In formula (III): X is F; R 1 is Cl or F; R 2 It is any one of F, Cl, CF3, and NO2.

3. The method according to claim 1 N -Application of pyridylbenzothiazole compounds in weed control.

4. The use according to claim 3, characterized in that described N -Pyridylbenzothiazole compounds are used to control broadleaf weeds and / or grass weeds.

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

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

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