A compound containing a triazolinone structure, a preparation method thereof and application thereof as a herbicide

Abstract

The application discloses a triazolinone compound, and a preparation method thereof. The structural general formula (I) of the triazolinone compound is as follows: the preparation method is to perform esterification or amidation reaction on a compound containing a hydroxyl group or an amino group as raw material in a solvent and 2-chloro-3-(2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo-1,2,4-triazol-1-yl)-4-fluorophenyl) propionyl chloride prepared through acyl chloride reaction, so as to obtain a triazolinone structure-containing herbicidal compound. The preparation method is simple, the reaction process is short, and the triazolinone structure-containing herbicidal compound has the advantages of novel structure, high herbicidal activity and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of pesticide chemistry, and discloses a compound containing a triazolinone structure, a preparation method thereof and application thereof as a herbicide. BACKGROUND

[0002] Weeds compete with crops for light, water and living space, spread diseases and pests, and seriously affect the yield and quality of crops, which is one of the biological disasters threatening agricultural production. Chemical weeding has the advantages of complete weeding, time and labor saving, and low cost, and has become the main means of preventing weeds. However, in recent years, with the continuous strengthening of people's environmental protection consciousness, the succession of weed populations and the development of their resistance to chemical pesticides, green and safe herbicide compounds with unique mechanisms have become an urgent need for agricultural production.

[0003] Triazolinone is an important herbicide, which has a very broad application prospect due to its small dosage, fast weeding and the like. At present, the commercialized herbicide varieties based on the structure of triazolinone include amicarbazone, propyrisulfuron, mesosulfuron, cloquintocet-mexyl and the like. Through literature search, WO9002120 discloses the synthesis and biological activity of a triazolinone herbicide. The patent CN106831618A discloses a quaternary ammonium salt compound and its application, which includes a quaternary ammonium salt compound of triazolinone herbicide, and has good surface activity and certain herbicidal activity. The triazolinone herbicide has good activity on the weeds resistant to sulfonylurea herbicides, and therefore, it is of great significance to develop triazolinone herbicide compounds. SUMMARY

[0004] In order to overcome the deficiencies of the prior art, the present inventors have introduced a series of functional groups (such as phenoxy carboxylic acid group) into the structure of the triazolinone herbicide lead compound, thereby increasing the target site of the new compound for weeding; on the other hand, starting from non-target resistance, a series of plant endogenous products (such as amino acid ester) are introduced to enhance the phloem transport and conduction capacity of the triazolinone herbicide. With the increasingly prominent problem of resistant weeds, novel herbicide varieties with novel structure and unique mechanism have become an urgent need in the market, and therefore, the development of herbicide compounds containing multiple functional groups based on the triazolinone structure as the active lead group will have good application prospect.

[0005] Specifically, the first aspect of the present application provides a herbicide compound containing a triazolinone structure, and the structure general formula is shown as formula (I):

[0006]

[0007] In formula (I), R represents a hydrazine group, an acylhydrazine group, an alkylamine group, a substituted aromatic amine group, a substituted phenoxy group or a substituted amino acid ester group.

[0008] Preferably, the hydrazine group is -NHNH2;

[0009] Preferably, the hydrazide group is -NHNHCOO(CH2)nCH3, n is 1-7; n CH3, n is 1-7;

[0010] Preferably, the alkylamine group is -NH(CH2)nCH3, n is 3-7; n CH3, n is 3-7;

[0011] Preferably, the hydrogen on the aromatic ring of the substituted aromatic amine group is substituted by one or more of halogen, nitro, carboxyl, ester, methyl, isopropyl, propenyl or methoxy;

[0012] Preferably, the hydrogen on the aromatic ring of the substituted phenoxy group is substituted by one or more of halogen, nitro, carboxyl, ester, methyl, isopropyl, propenyl or methoxy;

[0013] Preferably, the substituent of the substituted amino acid ester group is methyl or benzyl.

[0014] The second aspect of the present application is to provide a preparation route of the compound shown in formula (I): 2-chloro-3-(2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo-1,2,4-triazol-1-yl)-4-fluorophenyl)propionic acid (III) is reacted by acyl halide to obtain 2-chloro-3-(2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo-1,2,4-triazol-1-yl)-4-fluorophenyl)propionyl chloride (II). The above compound (II) is reacted with a reactant C in the presence of an acid-binding agent by esterification or amidation to obtain the compound shown in formula (I).

[0015] The reaction formula is as follows:

[0016]

[0017] The specific preparation method of the present application comprises the following steps:

[0018] 1) A certain proportion of compound (III) is dissolved in an acyl halide reaction solvent, an acyl halide reagent dissolved in an acyl halide reaction solvent is added dropwise, and the reaction is stirred for a certain time until the end point, and then the product (II) is obtained by desolventization and purification;

[0019] 2) A certain proportion of reactant C and an acid-binding agent are sequentially added to an esterification or amidation reaction solvent, and the temperature is controlled and stirred uniformly, the esterification (amidation) reaction solvent dissolved with the product (II) is added dropwise to the reaction system, and the temperature is continuously controlled and stirred until the end point of the reaction, and then the product (I) is obtained by water washing, desolventization and purification.

[0020] In the preparation method, the reactant C is hydrazine, hydrazide, alkylamine or aromatic amine, substituted phenol or substituted amino acid ester;

[0021] The number of carbon atoms of the hydrazide is 2-8, and the hydrazide can be specifically acetylhydrazide, propionylhydrazide, butyrylhydrazide, valerylhydrazide, caproylhydrazide, heptylhydrazide or octanoylhydrazide;

[0022] The number of carbon atoms of the alkylamine group is 4-8, and the alkylamine can be specifically butylamine, pentylamine, hexylamine, heptylamine or octylamine;

[0023] The aromatic amine can be specifically p-chloroaniline, p-methyl aniline, p-nitroaniline, p-aminobenzoic acid, 3-amino-4-chlorobenzoic acid, 4-amino-5-chloro-2-ethoxybenzoic acid or methyl o-aminobenzoate;

[0024] The substituted phenol can be specifically 4-nitrophenol, methyl 2-hydroxybenzoate, methyl p-hydroxybenzoate, 4-allyl-2-methoxyphenol, 5-isopropyl-2-methylphenol or 2-hydroxy-3,5-dinitrobenzoic acid;

[0025] The amino acid ester is alanine ethyl ester, glycine methyl ester, 4-aminobutyric acid ethyl ester or phenylalanine ethyl ester.

[0026] The acyl halide reagent is selected from one of oxalyl chloride, sulfurous chloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide;

[0027] The acyl halide reaction solvent is selected from one or more of chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, tetrahydrofuran or dioxane, and preferably dichloromethane;

[0028] In the acyl halide reaction, the molar ratio of compound (III) to the acyl halide reagent is 1:(0.8-1.6), and preferably the molar ratio is 1:1.3;

[0029] The acyl halide reaction temperature is -5-100°C, and the optimal reaction temperature is 40°C;

[0030] The acyl halide reaction time is 0.5-8 hours, and the optimal reaction time is 3 hours.

[0031] The esterification or amidation reaction solvent can be one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide;

[0032] In the esterification or amidation reaction, the acid binding agent can be one of pyridine, triethylamine, tri-n-propylamine, tri-n-butylamine, N,N-diisopropylethylamine, 4-dimethylaminopyridine or tetramethyl ethylenediamine, and preferably triethylamine;

[0033] The molar ratio of compound (II), reactant C and acid binding agent in the esterification or amidation reaction is 1: (0.8-2): (0-2), and the optimal molar ratio is 1:1.1:1.1;

[0034] The esterification or amidation reaction temperature is 0-100℃, and the optimal reaction temperature is 25-60℃;

[0035] The esterification or amidation reaction time is 1-12 hours, and the optimal reaction time is 2-6 hours.

[0036] The third aspect of the present application also provides the use of the compound shown in formula (I) as a herbicide.

[0037] The present application can achieve the technical effects are:

[0038] 1. The preparation method provided by the present application is simple, and the reaction process is short.

[0039] 2. The herbicidal compound provided by the present application contains a triazolinone structure, and has novel structure, high herbicidal activity and many other advantages. DETAILED DESCRIPTION

[0040] The technical content of the present application is further illustrated by the following specific examples, but it does not mean to limit the present application.

[0041] In the following examples, the experimental methods used are conventional methods unless otherwise specified.

[0042] In the following examples, the materials, reagents, etc. used are commercially available unless otherwise specified.

[0043] Table 1 is the structure of the reactant in the examples

[0044] Table 1 is the structure of the reactant C

[0045]

[0046]

[0047] Example 1

[0048] (1) Into a 50 mL reaction flask, 2-chloro-3-(2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo- 1,2,4-triazol-l-yl)-4-fluorophenyl)propionic acid (III) 13 mmol and dichloromethane 15 mL were added, and a solution of thionyl chloride 16.9 mmol in dichloromethane 10 mL was added dropwise with stirring, and the reaction was heated to 40°C for 3 hours. The reaction was nearly complete, and 2-chloro-3-(2-chloro-5-(4-difluoromethyl-3-methyl-5-oxo-l,2,4-triazol-l-yl)-4- fluorophenyl)propionyl chloride (II) was obtained by distilling off the solvent under reduced pressure and storing in a refrigerator.

[0049] (2) Into a 50 mL reaction flask, p-nitroaniline 2.1 mmol and tetrahydrofuran 15 mL were added, and stirring was performed until complete dissolution, and triethylamine 2.1 mmol was added as an acid-binding agent. The reaction system was cooled to 0-4°C in an ice bath, and a solution of intermediate acyl chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise, and stirring was performed overnight for 12 hours. After the reaction was completed, the reaction was poured into water and diluted with dilute hydrochloric acid to adjust the pH to be acidic, and extracted with ethyl acetate, and washed with water 3 times, and the organic phase was dried with anhydrous magnesium sulfate, and filtered and distilled off the solvent under reduced pressure to obtain the product 1, which was recrystallized in ethyl acetate to obtain a yellow solid. The reaction yield was 83.7%, and the product content was 98.2%.

[0050]

[0051] Example 2

[0052] Into a 50 mL reaction flask, p-chloroaniline 2.2 mmol and dichloromethane 15 mL were added, and stirring was performed until complete dissolution, and triethylamine 2.2 mmol was added as an acid-binding agent. The reaction system was cooled to 0-4°C in an ice bath, and a solution of intermediate acyl chloride (II) 2.0 mmol in dichloromethane 5 mL was added dropwise, and the ice bath was removed, and the reaction was heated to 40°C for 4 hours. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust the pH to be acidic, and extracted with ethyl acetate, and washed with water 3 times, and the organic phase was dried with anhydrous magnesium sulfate, and distilled off the solvent under reduced pressure to obtain the product 2, which was recrystallized in ethyl acetate to obtain a white solid. The reaction yield was 85.2%, and the product content was 98.5%.

[0053]

[0054] Example 3

[0055] Into a 50 mL reaction flask, 2.2 mmol of p-toluidine and 15 mL of tetrahydrofuran were added, and after stirring until complete dissolution, 2.2 mmol of triethylamine was added. The reaction system was cooled to 0-4°C in an ice bath, and 2.0 mmol of the intermediate acyl chloride (II) dissolved in 5 mL of tetrahydrofuran was slowly added dropwise. The ice bath was removed, and the reaction was heated to 40°C for 4 hours. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust the pH to acidic, and extraction was performed with ethyl acetate. After washing with water three times, the organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain the product 3 as a white solid after recrystallization in ethyl acetate. The reaction yield was 82.5%, and the product content was 98.1%.

[0056]

[0057] Example 4

[0058] Into a 50 mL reaction flask, 2.6 mmol of 2,4-dinitroaniline and 15 mL of N,N-dimethylformamide were added, and after stirring until complete dissolution, 2.6 mmol of triethylamine was added. The reaction system was cooled to 0-4°C in an ice bath, and 2.0 mmol of the intermediate acyl chloride (II) dissolved in 5 mL of N,N-dimethylformamide was slowly added dropwise. The reaction was heated to 60°C for 4 hours. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust the pH to acidic, and extraction was performed with ethyl acetate. After washing with water three times, the organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain the product 4 as a yellow solid after recrystallization in ethyl acetate. The reaction yield was 69.4%, and the product content was 98.8%.

[0059]

[0060] Example 5

[0061] Into a 50 mL reaction flask, 1.8 mmol of methyl anthranilate and 15 mL of tetrahydrofuran were added, and after stirring until complete dissolution, 2.0 mmol of triethylamine was added. The reaction system was cooled to 0-4°C in an ice bath, and 2.0 mmol of the intermediate acyl chloride (II) dissolved in 5 mL of tetrahydrofuran was slowly added dropwise. Stirring was performed at room temperature for 3 hours. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust the pH to acidic, and extraction was performed with ethyl acetate. After washing with water three times, the organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain the product 5 as a light yellow solid after recrystallization in dichloromethane. The reaction yield was 80.4%, and the product content was 98.6%.

[0062]

[0063] Example 6

[0064] To a 50 mL reaction flask was added 3-amino-4-chlorobenzoic acid 1.8 mmol and dimethyl sulfoxide 20 mL, after stirring to complete dissolution, triethylamine 4.0 mmol was added. The reaction system was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol was dissolved in dimethyl sulfoxide 5 mL and slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. The pH was adjusted to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, washed with water 3 times and saturated sodium bicarbonate 3 times, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain product 6.

[0065]

[0066] The reaction yield was 73.4%.

[0067] Example 7

[0068] To a 50 mL reaction flask was added 3-amino-4-chlorobenzoic acid 1.8 mmol and dimethyl sulfoxide 20 mL, after stirring to complete dissolution, triethylamine 4.0 mmol was added. The reaction system was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol was dissolved in dimethyl sulfoxide 5 mL and slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. The pH was adjusted to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, washed with water 3 times and saturated sodium bicarbonate 3 times, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain product 6.

[0069]

[0070] Example 8

[0071] To a 50 mL reaction flask was added 3-amino-4-chlorobenzoic acid 1.8 mmol and dimethyl sulfoxide 20 mL, after stirring to complete dissolution, triethylamine 4.0 mmol was added. The reaction system was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol was dissolved in dimethyl sulfoxide 5 mL and slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. The pH was adjusted to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, washed with water 3 times and saturated sodium bicarbonate 3 times, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain product 6.

[0072]

[0073] The reaction yield was 73.4%.

[0074] Example 9

[0075] Into a 50 mL reaction flask, 2-hydroxybenzoic acid methyl ester 1.8 mmol and tetrahydrofuran 15 mL were added, after stirring to complete dissolution, triethylamine 2.2 mmol was added. The reaction system temperature was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in tetrahydrofuran 5 mL was slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. Adjust the pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain the product 9. The reaction yield was 80.7%.

[0076]

[0077] Example 10

[0078] Into a 50 mL reaction flask, 4-nitrophenol 1.9 mmol and tetrahydrofuran 15 mL were added, after stirring to complete dissolution, triethylamine 2.0 mmol was added. The reaction system temperature was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in tetrahydrofuran 5 mL was slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. Adjust the pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate and then washed with saturated sodium bicarbonate solution, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain the product 10, which was recrystallized in ethyl acetate to obtain a light yellow solid. The reaction yield was 81.7%, and the product content was 92.6%.

[0079]

[0080] Example 11

[0081] Into a 50 mL reaction flask, 4-hydroxybenzoic acid methyl ester 1.9 mmol and tetrahydrofuran 15 mL were added, after stirring to complete dissolution, triethylamine 2.0 mmol was added. The reaction system temperature was reduced to 0-4°C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in tetrahydrofuran 5 mL was slowly added dropwise, after stirring at room temperature for 4 hours, the reaction reached the end point. Adjust the pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, the organic phase was dried with anhydrous magnesium sulfate, filtered and then distilled to remove the solvent under reduced pressure to obtain the product 11. The reaction yield was 81.7%.

[0082]

[0083] Example 12

[0084] A 50 mL reaction flask was charged with 4-allyl-2-methoxyphenol 1.8 mmol and tetrahydrofuran 15 mL, after stirring to complete dissolution, triethylamine 2.4 mmol was added. The reaction system temperature was reduced to 0-4 °C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in tetrahydrofuran 5 mL was added dropwise slowly, after stirring at room temperature for 6 hours, the reaction reached the end point. Adjusted pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, the organic phase was washed with deionized water 3 times,

[0085] The organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain product 12. The reaction yield was 79.2%.

[0086]

[0087] Example 13

[0088] A 50 mL reaction flask was charged with 5-isopropyl-2-methylphenol 1.9 mmol and tetrahydrofuran 15 mL, after stirring to complete dissolution, triethylamine 2.4 mmol was added. The reaction system temperature was reduced to 0-4 °C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in tetrahydrofuran 5 mL was added dropwise slowly, after stirring at room temperature for 6 hours, the reaction reached the end point. Adjusted pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate, the organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain product 13. The reaction yield was 82.3%.

[0089]

[0090]

[0091] Example 14

[0092] A 50 mL reaction flask was charged with 2-hydroxy-3,5-dinitrobenzoic acid 2.3 mmol and dimethyl sulfoxide 15 mL, after stirring to complete dissolution, triethylamine 4 mmol was added. The reaction system temperature was reduced to 0-4 °C by ice bath, intermediate acid chloride (II) 2.0 mmol dissolved in dimethyl sulfoxide 5 mL was added dropwise slowly, after stirring at room temperature for 3 hours, the reaction reached the end point. Adjusted pH to acidic by adding dilute hydrochloric acid dropwise, extracted with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, filtered, and then distilled to remove the solvent under reduced pressure to obtain product 14. The reaction yield was 73.3%.

[0093]

[0094] Example 15

[0095] A 50 mL reaction flask was charged with hydrazine hydrate 4.0 mmol and tetrahydrofuran 3 mL, the reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in dimethyl sulfoxide 5 mL was added dropwise with stirring. The reaction was stirred at room temperature for 0.5 h, and then extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate solution three times, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to give white solid product 15. The reaction yield was 60%, and the product content was 98.2%.

[0096]

[0097] Example 16

[0098] A 50 mL reaction flask was charged with octanohydrazide 2.6 mmol and tetrahydrofuran 15 mL, and stirred until completely dissolved. Triethylamine 2.4 mmol was added, and the reaction system was cooled to 0-4 °C in an ice bath. Intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise with stirring. The reaction was stirred at room temperature for 2 h, and then diluted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate solution three times, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to give product 16. The product was recrystallized from dichloromethane to give a light yellow solid. The reaction yield was 80.3%, and the product content was 98.5%.

[0099]

[0100]

[0101] Example 17

[0102] A 50 mL reaction flask was charged with n-butylamine 2.6 mmol and dichloromethane 15 mL, and stirred until completely dissolved. Triethylamine 2.2 mmol was added, and the reaction system was cooled to 0-4 °C in an ice bath. Intermediate acid chloride (II) 2.0 mmol in dichloromethane 5 mL was added dropwise with stirring. The reaction was stirred at room temperature for 2 h, and then diluted with ethyl acetate. The organic phase was washed with saturated aqueous sodium bicarbonate solution three times, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to give yellow viscous liquid product 17. The reaction yield was 89.1%, and the product content was 98.2%.

[0103]

[0104] Example 18

[0105] To a 50 mL reaction flask was added glycine methyl ester 3.0 mmol and tetrahydrofuran 15 mL. After stirring to complete dissolution, triethylamine 3.0 mmol was added. The reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise slowly. The reaction was allowed to proceed at room temperature for 6 hours until the reaction endpoint was reached. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust to acidic, and extraction was performed with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, filtered, and then desolved by distillation under reduced pressure to obtain product 19. The reaction yield was 84.1%.

[0106]

[0107] Example 19

[0108] To a 50 mL reaction flask was added glycine methyl ester 3.0 mmol and tetrahydrofuran 15 mL. After stirring to complete dissolution, triethylamine 3.0 mmol was added. The reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise slowly. The reaction was allowed to proceed at room temperature for 6 hours until the reaction endpoint was reached. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust to acidic, and extraction was performed with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, filtered, and then desolved by distillation under reduced pressure to obtain product 19. The reaction yield was 84.1%.

[0109]

[0110]

[0111] Example 20

[0112] To a 50 mL reaction flask was added glycine methyl ester 3.0 mmol and tetrahydrofuran 15 mL. After stirring to complete dissolution, triethylamine 3.0 mmol was added. The reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise slowly. The reaction was allowed to proceed at room temperature for 6 hours until the reaction endpoint was reached. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust to acidic, and extraction was performed with ethyl acetate. The organic phase was dried with anhydrous magnesium sulfate, filtered, and then desolved by distillation under reduced pressure to obtain product 19. The reaction yield was 84.1%.

[0113]

[0114] After filtration, the product 20 was obtained by distillation under reduced pressure. The reaction yield was 80.3%.

[0115] Example 21

[0116] Into a 50 mL reaction flask was added ethyl 4-aminobutyrate 3.0 mmol and tetrahydrofuran 15 mL, after stirring to complete dissolution, triethylamine 3.0 mmol was added. The reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise slowly. The reaction was allowed to proceed at room temperature for 6 hours to reach the end point. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust to acidic, extracted with ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, filtered and then distilled under reduced pressure to remove the solvent to obtain the product 21 as a light yellow solid. The reaction yield was 81.5%, and the product content was 95.5%.

[0117]

[0118] Product content 95.5%.

[0119] Example 22

[0120] Into a 50 mL reaction flask was added ethyl 4-aminobutyrate 3.0 mmol and tetrahydrofuran 15 mL, after stirring to complete dissolution, triethylamine 3.0 mmol was added. The reaction system was cooled to 0-4 °C in an ice bath, and intermediate acid chloride (II) 2.0 mmol in tetrahydrofuran 5 mL was added dropwise slowly. The reaction was allowed to proceed at room temperature for 6 hours to reach the end point. After the reaction was completed, dilute hydrochloric acid was added dropwise to adjust to acidic, extracted with ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, filtered and then distilled under reduced pressure to remove the solvent to obtain the product 21 as a light yellow solid. The reaction yield was 81.5%, and the product content was 95.5%.

[0121]

[0122] Example 23

[0123] Herbicidal activity determination: The herbicidal activity of the compounds of the present application was evaluated by pot stem-leaf treatment experiment.

[0124] The amaranthus seeds were planted in a 9 cm diameter plastic pot, and the experimental soil was a mixture of vermiculite, nutrient soil and humus soil; after sowing, the soil was covered with 1 cm, and after watering, the greenhouse was cultured according to the conventional method. During the period, the seedlings were thinned twice to ensure that there were 8-10 amaranthus in each pot. At the 3-4 leaf stage of amaranthus, the compounds of the present application were dissolved in methanol and 2% Tween 80 was added and stirred uniformly, and then diluted with water to a certain concentration solution, and then sprayed, and the amount of each pot was 2 mL. The experiment was set up for 3 times, and after spraying, the greenhouse was cultured for one week to investigate the fresh weight inhibition rate of the compounds on amaranthus, and the calculation formula was:

[0125] Fresh weight inhibition rate (100%) = [(control weed fresh weight - treated weed fresh weight) / control weed fresh weight] x 100%

[0126] The fresh weight inhibition rate statistical results of the compounds on amaranthus are as follows in Table 2:

[0127] Table 2 Fresh weight inhibition rate statistical results of the compounds on amaranthus

[0128]

[0129]

[0130] Note: +++++, 100%. +++, > 90%. +++, > 80%. +++, > 70%. ++, > 60%. +, > 50%. -, < 50%.

Claims

1. A compound containing a triazolinone structure, the structural formula of which is shown in formula (Ⅰ): In formula (Ⅰ): R represents hydrazine group, acylhydrazine group, substituted phenoxy group, and amino acid ester group; The hydrazine group is -NHNH2; The hydrazide group is -NHNHCOO(CH2). n CH3, n can be 1 to 7; The hydrogen atom on the substituted phenoxy benzene ring is replaced by one or more of the following groups: halogen, nitro, carboxyl, ester, methyl, isopropyl, propenyl, or methoxy, wherein... The ester group is formed when a hydrogen atom on the benzene ring is replaced by a methyl formate group, and the methyl formate group is in the ortho or para position; The amino acid ester group is alanine ethyl ester group, glycine methyl ester group, 4-aminobutyric acid ethyl ester group or phenylalanine ethyl ester group; The preparation steps of the triazolinone-containing compound (Ⅰ) are as follows: 1) Dissolve a certain proportion of compound (Ⅲ) in an acyl halide reaction solvent, add dropwise an acyl halide reagent dissolved in the acyl halide reaction solvent, keep warm and stir the reaction until the endpoint, and obtain product (Ⅱ) after solvent removal and purification. 2) Add a certain proportion of reactant C and acid-binding agent to the esterification or amidation reaction solvent in sequence, control the temperature and stir evenly, add the esterification or amidation reaction solvent containing product (II) dropwise to the reaction system, continue to control the temperature and stir until the reaction endpoint, and obtain product (I) after washing with water, desolventizing and purifying. The acid-binding agent in the esterification or amidation reaction is triethylamine; In the esterification or amidation reaction, the molar ratio of compound (II), reactant C, and acid-binding agent is 1:1.1:1.1; The esterification or amidation reaction temperature is 25℃~60℃; The esterification or amidation reaction takes 2 to 6 hours.

2. The triazolinone-containing compound according to claim 1, wherein the acyl halide reagent is selected from one of oxalyl chloride, thionyl chloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, or phosphorus pentabromide; The solvent for the acylhalogenation reaction is selected from one or more of chloroform, dichloromethane, carbon tetrachloride, n-hexane, benzene, toluene, ethyl acetate, tetrahydrofuran, or dioxane; In the acyl halide reaction, the molar ratio of compound (Ⅲ) to the acyl halide reagent is 1:(0.8-1.6); The acyl halide reaction temperature is -5 to 40°C; The acylhalogenation reaction time is 0.5 to 8 hours.

3. The triazolinone-containing compound according to claim 2, wherein the acyl halide reagent is thionyl chloride, the acyl halide reaction solvent is dichloromethane, the molar ratio of compound (III) to the acyl halide reagent in the acyl halide reaction is 1:1.3, the acyl halide reaction temperature is 30℃~40℃, and the acyl halide reaction time is 2~4 hours.

4. The triazolone-containing compound according to claim 1, wherein reactant C is hydrazine, acetylhydrazine, propionylhydrazine, butyrylhydrazine, valeratelhydrazine, hexanoylhydrazine, heptaylhydrazine, octanoylhydrazine, 4-nitrophenol, methyl 2-hydroxybenzoate, methyl p-hydroxybenzoate, 4-allyl-2-methoxyphenol, 5-isopropyl-2-methylphenol, 2-hydroxy-3,5-dinitrobenzoic acid, ethyl alanine, methyl glycine, ethyl 4-aminobutyrate, or ethyl phenylalanine. The solvent for the esterification or amidation reaction in the preparation method is one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, or dimethyl sulfoxide.

5. The application of the compound of formula (Ⅰ) according to claim 1 as a weed control agent.

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