Pyrimidinedione derivative containing isoxazoline as well as preparation method and application of pyrimidinedione derivative

Abstract

The invention provides an isoxazoline-containing pyrimidinedione derivative as well as a preparation method and application thereof, and belongs to the technical field of organic matter preparation. According to the invention, chemical modification and molecular design are carried out on a compound with a pyrimidinedione structure, and a substituent group is introduced to methylene connected with an ester group, so that a series of efficient compounds which can be used for agricultural or forestry weeding and have excellent activity are obtained, and particularly, the compounds have very good biological activity on gramineous weeds, broadleaf weeds and other weeds.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic matter preparation, and particularly relates to a pyrimidine dione derivative containing isoxazoline and a preparation method and application thereof. BACKGROUND

[0002] As an indispensable plant protection means in modern agricultural system, herbicides significantly improve crop yield by inhibiting the growth of weeds in the field. Protoporphyrinogen oxidase (PPO) as a key enzyme in the biosynthesis pathway of chlorophyll and hemoglobin, is responsible for the oxidative conversion process of protoporphyrinogen IX to protoporphyrin IX, and has become one of the core action targets for herbicide research and development. It is worth noting that PPO inhibitor herbicides not only show broad-spectrum and high-efficiency herbicidal activity, but also have the advantages of good environmental compatibility and low dosage. Among them, the new PPO inhibitor represented by pyrimidine dione provides a potential lead structure for new pesticide creation due to its unique molecular skeleton and mechanism of action. Therefore, it is of great significance to obtain a pyrimidine dione derivative containing isoxazoline and a preparation method and application thereof. SUMMARY

[0003] The purpose of the present application is to provide a pyrimidine dione derivative containing isoxazoline and a preparation method and application thereof, so as to solve the problem of drug resistance of traditional herbicides in the prior art.

[0004] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical scheme:

[0005] The present application provides a pyrimidine dione derivative containing isoxazoline, and the structural formula of the pyrimidine dione derivative is shown as formula I:

[0006]

[0007] Among them, R is selected from halogen, cyano, nitro, amino, C1-C6 alkyl, aryl, oxygen-containing alkyl, unsaturated alkyl, aryl-containing alkyl, heteroaryl, C3-C6 cycloalkyl and heteroatom-containing hydrocarbon group.

[0008] The present application also provides a preparation method of the pyrimidine dione derivative containing isoxazoline, comprising the following steps:

[0009] (1) condensation reaction is carried out by taking 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester and dimethylcarbamoyl chloride as main raw materials to obtain 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester;

[0010] (2) mixing 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester, 5-amino-2-chloro-4-fluorobenzoic acid allyl ester and acetic acid to carry out a first reaction, to obtain 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester;

[0011] (3) mixing 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester, potassium iodide and potassium carbonate in a solvent to carry out a second reaction, and detecting by TLC until the reaction is completed, to obtain 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester;

[0012] (4) mixing 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester and N-chlorosuccinimide to carry out a third reaction, and finally adding triethylamine and an oxime compound to carry out a fourth reaction, to obtain a pyrimidinedione derivative containing an isoxazoline.

[0013] The application also provides an application of the pyrimidinedione derivative containing an isoxazoline as described above as a herbicide or a herbicide compound.

[0014] The application also provides an application of the pyrimidinedione derivative containing an isoxazoline as described above in preparation of wettable powder, wettable liquid, soluble powder, dispersible liquid, aqueous solution, microemulsion, emulsion, water emulsion, sprayable solution, suspension, dispersible oil suspension, powder, microcapsule suspension, water dispersible granule, water soluble granule, granule for sowing and soil application, aerosol, ultra-low volume agent or wax product.

[0015] The application has the following beneficial effects:

[0016] The application introduces a substituent on the methylene group connected with the ester group through chemical modification and molecular design of a compound having a pyrimidinedione structure, to obtain a series of compounds having excellent activity and being applicable to agricultural or forestry weed control, especially having good biological activity on weeds such as gramineae and broadleaf weeds.

[0017] The obtained compound shows excellent control effect on various weeds when used at a lower concentration, and also shows excellent control activity on weeds having resistance to traditional herbicides. DETAILED DESCRIPTION

[0018] The present application provides a kind of isoxazoline-containing pyrimidine dione derivative, the structural formula of the pyrimidine dione derivative is as shown in formula I:

[0019]

[0020] Wherein, R is selected from halogen, cyano, nitro, amino, C1-C6 alkyl, aromatic group, oxygen-containing alkyl, unsaturated alkyl, aromatic group-containing alkyl, heteroaromatic group, C3-C6 cycloalkyl and heteroatom-containing hydrocarbon group.

[0021] In the present application, the oxygen-containing alkyl includes C1-C6 alkoxy, carbonyl, formyl, alkylcarbonyl, alkoxycarbonyl; the unsaturated alkyl includes C2-C6 alkenyl or C2-C6 alkynyl; the aromatic group-containing alkyl includes aromatic group alkyl or heteroaromatic group alkyl; and the heteroatom-containing hydrocarbon group includes halogenated alkyl, cyanoalkyl, halogenated alkenyl, halogenated alkynyl, alkylthio, halogenated alkylthio, halogenated alkoxy, halogenated alkylcarbonyl, halogenated alkoxycarbonyl, alkylaminoalkyl, halogenated alkylaminoalkyl or halogenated alkoxyalkyl.

[0022] In the present application, the pyrimidine dione derivative is selected from one of the following S1-S40 compounds:

[0023]

[0024]

[0025]

[0026]

[0027] The present application also provides a preparation method of the isoxazoline-containing pyrimidine dione derivative described above, comprising the following steps:

[0028] (1) performing condensation reaction with 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester and dimethylcarbamoyl chloride as main raw materials to obtain 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester;

[0029] (2) mixing 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester, 5-amino-2-chloro-4-fluorobenzoic acid allyl ester and acetic acid, and then performing first reaction to obtain 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester;

[0030] (3) mixing 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester, potassium iodide and potassium carbonate in a solvent to perform a second reaction, and detecting by TLC until the reaction is completed to obtain 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester;

[0031] (4) mixing 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester and N-chlorosuccinimide to perform a third reaction, and finally adding triethylamine and an oxime compound to perform a fourth reaction to obtain an isoxazoline-containing pyrimidinedione derivative.

[0032] In the present application, in step (1), the solvent used in the condensation reaction is N,N-dimethylformamide; the raw material of the condensation reaction further comprises sodium hydride; the molar ratio of the sodium hydride, 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester and dimethylcarbamoyl chloride is 1.3-1.7:1:1.2-1.7, preferably 1.4-1.6:1:1.3-1.6, and further preferably 1.5:1:1.5.

[0033] In the present application, the specific process of the condensation reaction is as follows: mixing sodium hydride and N,N-dimethylformamide (DMF), adding 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester dropwise into the above bottle to stir to obtain a mixed solution, mixing dimethylcarbamoyl chloride with DMF, and slowly adding the mixture into the above mixed solution under ice bath to stir to obtain 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester; the temperature of the stirring reaction is independently 20-30°C, and the time of the stirring reaction is independently 0.5-10 h.

[0034] The reaction formula of step (1) is as follows:

[0035]

[0036] In the present application, after the condensation reaction is completed, extraction, drying and concentration are sequentially performed; the reagent used in the extraction is preferably ethyl acetate; the drying is preferably drying with anhydrous sodium sulfate; and the concentration is preferably vacuum concentration, and the vacuum degree is preferably 0.098 MPa.

[0037] In the present application, in step (2), the molar ratio of the 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester and the 5-amino-2-chloro-4-fluorobenzoic acid allyl ester is 1:1.0-1.5, preferably 1:1.1-1.4, and further preferably 1:1.2-1.3; the temperature of the first reaction is 30-150°C, preferably 80-130°C, and further preferably 100-125°C; and the time of the first reaction is 0.5-10h, preferably 3-9h, and further preferably 5-7h.

[0038] The reaction formula of step (2) is:

[0039]

[0040] In the present application, after the first reaction, washing, extraction, drying, concentration and purification are sequentially performed; the reagent for the washing is preferably deionized water, and the number of washing is preferably 3-5 times, and further preferably 4 times; the reagent for the extraction is preferably ethyl acetate; the drying is preferably dried with anhydrous sodium sulfate; the concentration is preferably vacuum concentration, and the vacuum degree is preferably 0.098MPa; and the purification is preferably column chromatography purification.

[0041] In the present application, in step (3), the molar ratio of the 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester, potassium iodide and potassium carbonate is 1:1.0-1.4:1.0-1.4, preferably 1:1.1-1.3:1.1-1.3, and further preferably 1:1.2:1.2; the temperature of the second reaction is 30-50°C, and the time of the second reaction is 0.5-10h.

[0042] The reaction formula of step (3) is:

[0043]

[0044] In the present application, after the second reaction, washing, extraction, drying, concentration and purification are sequentially performed; the reagent for the washing is preferably water, and the number of washing is preferably 3-5 times, and further preferably 4 times; the reagent for the extraction is preferably ethyl acetate; the drying is preferably dried with anhydrous sodium sulfate; the concentration is preferably vacuum concentration, and the vacuum degree is preferably 0.098MPa; and the purification is preferably column chromatography purification.

[0045] In the present application, in step (4), the amount ratio of the 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester, N-chlorosuccinimide, triethylamine and the oxime compound is 1:1.3-1.7:1.3-1.7:1.0-1.4, preferably 1:1.4-1.6:1.4-1.6:1.1-1.3, and more preferably 1:1.5:1.5:1.2;

[0046] The structure of the oxime compound is shown in Formula II:

[0047]

[0048] wherein R is selected from halogen, cyano, nitro, amino, C1-C6 alkyl, aryl, oxygen-containing alkyl, unsaturated alkyl, aryl-containing alkyl, heteroaryl, C3-C6 cycloalkyl and heteroatom-containing hydrocarbon group.

[0049] In the present application, in step (4), the temperature of the third reaction is 20-50°C, and the time of the third reaction is 0.5-8h; the temperature of the fourth reaction is 20-30°C, and the time of the fourth reaction is 0.5-6h.

[0050] The reaction formula of step (4) is:

[0051]

[0052] In the present application, after the fourth reaction, washing, extraction, drying, concentration and purification are sequentially performed; the reagent for washing is preferably water, and the number of washing is preferably 3-5 times, and more preferably 4 times; the reagent for extraction is preferably ethyl acetate; the drying is preferably anhydrous sodium sulfate drying; the concentration is preferably vacuum concentration, and the vacuum degree is preferably 0.098 MPa; and the purification is preferably column chromatography purification.

[0053] The present application also provides the use of the above-mentioned isoxazoline-containing pyrimidinedione derivative as a herbicide or herbicide complexing agent.

[0054] In the present application, the amount of the isoxazoline-containing pyrimidinedione derivative is preferably 1-1000 g a.i. / ha, more preferably 1-500 g a.i. / ha, and more preferably 1-100 g a.i. / ha.

[0055] In the present application, the object of the herbicide application includes various weeds, preferably Amaranthus retroflexus, Abutilon theophrasti or Setaria viridis.

[0056] In the present application, the isoxazoline-containing pyrimidinedione derivative can be used as a herbicide complexing agent in combination with other kinds of herbicides, and there is no particular limitation on the kind of the other herbicides, and known kinds of herbicides disclosed in the prior art can be used.

[0057] The present application also provides use of the above-mentioned isoxazoline-containing pyrimidinedione derivative in the preparation of wettable powder, wettable liquid, soluble powder, dispersible liquid, aqueous solution, microemulsion, emulsion, aqueous emulsion, sprayable solution, suspension, dispersible oil suspension, powder, microcapsule suspension, water dispersible granule, water soluble granule, granule for sowing and soil application, aerosol, ultra-low volume agent or wax product.

[0058] The technical solutions provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0059] The preparation process of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester used in the examples is as follows:

[0060] (1) Preparation of 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester:

[0061] Add 81.91 mmol of sodium hydride and 50 mL of N,N-dimethylformamide (DMF) into a 100 mL round-bottom flask, drop 54.61 mmol of 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester into the above flask and stir the reaction at 25°C for 1 h, mix 81.91 mmol of dimethylaminocarbonyl chloride with 50 mL of DMF, slowly drop the mixture into the above solution under ice bath condition, stir the reaction at 25°C for 10 h, after the reaction is completed, perform vacuum concentration (vacuum degree is 0.098 MPa), extract with ethyl acetate, dry with anhydrous sodium sulfate, and purify by column chromatography to obtain 6.94 g of yellow liquid, with a yield of 50%. 1 H NMR (600 MHz, DMSO-d6) δ 9.22 (s, 1H), 5.88 (s, 1H), 4.14 (q, J = 7.1 Hz, 2H), 2.93 (s, 6H), 1.21 (t, J = 7.1 Hz, 3H).

[0062] (2) Preparation of 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester:

[0063] Into a 100 mL round bottom flask, 19.67 mmol of 3-(3,3-dimethylureido)-4,4,4- trifluorobut-2-enoic acid ethyl ester and 23.60 mmol of 5-amino-2-chloro-4-fluorobenzoic acid allyl ester were added, 100 mL of acetic acid was added, heated to 80°C, stirred for 6h, after the reaction was completed, extracted with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under vacuum (vacuum degree was 0.098 MPa), column chromatography purification to obtain 6.95 g of yellow liquid, the yield was 90%. 1 H NMR (600 MHz, DMSO-d6) δ 12.83 (s, 1H), 8.15 (d, J = 7.8 Hz, 1H), 7.89 (d, J = 9.5 Hz, 1H), 6.45 (s, 1H), 6.04 (ddt, J = 17.3, 10.9, 5.6 Hz, 1H), 5.44 (dq, J = 17.2, 1.5 Hz, 1H), 5.31 (dq, J = 10.5, 1.2 Hz, 1H), 4.84 (dt, J = 5.5, 1.4 Hz, 2H).

[0064] (3) Preparation of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)- 3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester:

[0065] Into a 100 mL round bottom flask, 12.73 mmol of 2-chloro-5-(2,6-dioxo-4- (trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester and 15.28 mmol of potassium iodide and 15.28 mmol of potassium carbonate were added, 50 mL of DMF was added, reacted at 30°C for 10h, TLC detection until the reaction was completed, extracted with ethyl acetate, dried over anhydrous sodium sulfate, concentrated under vacuum (vacuum degree was 0.098 MPa), column chromatography to obtain 4.87 g of yellow liquid, the yield was 94.0%. 1 H NMR (600 MHz, DMSO-d6) δ 8.06 (d, J = 7.7 Hz, 1H), 7.89 (d, J = 9.5 Hz, 1H), 5.76 (s, 1H), 4.26 (t, J = 6.5 Hz, 2H), 3.42 (s, 3H), 1.76 - 1.67 (m, 2H), 0.97 (td, J = 7.4, 2.7 Hz, 3H).

[0066] Example 1

[0067] Compound S1:

[0068]

[0069] Preparation of compound S1:

[0070] 0.74 mmol of allyl 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate and 1.11 mmol of N-chlorosuccinimide were added to a 100 mL round-bottom flask, and the mixture was stirred and reacted at 40°C for 40 minutes. Then, 0.89 mmol of 4-methylbenzaldehyde oxime and 1.11 mmol of triethylamine were added, and the mixture was stirred and reacted at 25°C for 5 hours. After the reaction, the mixture was washed with water three times, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated in vacuo (vacuum degree of 0.098 MPa). The mixture was purified by column chromatography to obtain 0.34 g of a yellow solid with a yield of 85%.

[0071] Example 2

[0072] Compound S2:

[0073]

[0074] Preparation of compound S2:

[0075] The difference from Example 1 is that benzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime. Other conditions are the same. Column chromatography purification gives 0.34 g of a yellow solid with a yield of 88%.

[0076] Example 3

[0077] Compound S4:

[0078]

[0079] Preparation of compound S4:

[0080] The difference from Example 1 is that 4-fluorobenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime. Other conditions are the same. Column chromatography purification gives 0.33 g of a yellow solid with a yield of 83%.

[0081] Example 4

[0082] Compound S8:

[0083]

[0084] Preparation of compound S8:

[0085] The difference from Example 1 is that 2,5-difluorobenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime. Other conditions are the same. Column chromatography purification gives 0.36 g of a yellow solid with a yield of 87%.

[0086] Example 5

[0087] Compound S9:

[0088]

[0089] Preparation of compound S9:

[0090] The difference from example 1 is that 2-chlorobenzaldoxime is used instead of 4-methylbenzaldoxime, and other conditions are the same. Yellow solid 0.37 g is obtained by column chromatography purification with the yield of 90%.

[0091] Example 6

[0092] Compound S12:

[0093]

[0094] Preparation of compound S12:

[0095] The difference from example 1 is that 4-(trifluoromethyl)benzaldoxime is used instead of 4-methylbenzaldoxime, and other conditions are the same. Yellow solid 0.34 g is obtained by column chromatography purification with the yield of 78%.

[0096] Example 7

[0097] Compound S13:

[0098]

[0099] Preparation of compound S13:

[0100] The difference from example 1 is that 2-methoxybenzaldoxime is used instead of 4-methylbenzaldoxime, and other conditions are the same. Yellow solid 0.33 g is obtained by column chromatography purification with the yield of 81%.

[0101] Example 8

[0102] Compound S14:

[0103]

[0104] Preparation of compound S14:

[0105] The difference from example 1 is that 2-(trifluoromethoxy)benzaldoxime is used instead of 4-methylbenzaldoxime, and other conditions are the same. Yellow solid 0.34 g is obtained by column chromatography purification with the yield of 75%.

[0106] Example 9

[0107] Compound S15:

[0108]

[0109] Preparation of compound S15:

[0110] The difference from Example 1 is that 4-fluoro-3-methylbenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same, and yellow solid 0.30 g is obtained by column chromatography purification, and the yield is 73%.

[0111] Example 10

[0112] Compound S16:

[0113]

[0114] Preparation of compound S16:

[0115] The difference from Example 1 is that acetaldoxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same, and yellow solid 0.31 g is obtained by column chromatography purification, and the yield is 92%.

[0116] Example 11

[0117] Compound S18:

[0118]

[0119] Preparation of compound S18:

[0120] The difference from Example 1 is that isobutyraldoxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same, and yellow solid 0.34 g is obtained by column chromatography purification, and the yield is 94%.

[0121] Example 12

[0122] Compound S19:

[0123]

[0124] Preparation of compound S19:

[0125] The difference from Example 1 is that 2,6-difluorobenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same, and yellow solid 0.33 g is obtained by column chromatography purification, and the yield is 79%.

[0126] Example 13

[0127] Compound S25:

[0128]

[0129] Preparation of compound S25:

[0130] The difference from Example 1 is that 4-(dimethylamino)benzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same, and yellow solid 0.27 g is obtained by column chromatography purification, and the yield is 65%.

[0131] Example 14

[0132] Compound S26:

[0133]

[0134] Preparation of compound S26:

[0135] The difference from Example 1 is that 2,4,5-trifluorobenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same. Yellow solid 0.38 g is obtained by column chromatography purification, and the yield is 88%.

[0136] Example 15

[0137] Compound S30:

[0138]

[0139] Preparation of compound S30:

[0140] The difference from Example 1 is that 2,6-dichlorobenzaldehyde oxime is used instead of 4-methylbenzaldehyde oxime, and other conditions are the same. Yellow solid 0.39 g is obtained by column chromatography purification, and the yield is 90%.

[0141] The H NMR data of compounds S1-S40 are detected respectively, and the detection results are shown in Table 1: 1 H NMR data of compounds S1-S40 are detected respectively, and the detection results are shown in Table 1:

[0142] Table 1 H NMR detection results of compounds S1-S40 1 H NMR detection results of compounds S1-S40 are detected respectively, and the detection results are shown in Table 1:

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] The post-emergence activity test is carried out on compounds S1-S40:

[0152] Spray method was used, and various weeds were used as the test objects. The weed seeds (Amaranthus retroflexus, Abutilon theophrasti or Setaria viridis) were evenly spread in 8x8 plastic pots filled with two-thirds of organic matter soil, and then placed in a room temperature environment for growth. When the grasses and broadleaf weeds grew to 2-3 leaf stage, the compounds S1-S40 were dissolved in DMSO, diluted to a dose of 37.5 g a.i. / ha, and sprayed on the plants using a spray pot. After the application, the plants were cultured in a greenhouse for three weeks, and the test results of the weeds were counted. The test was repeated three times, and the average value was taken. The test results are shown in Table 2.

[0153] The activity level standard of the biological activity evaluation, plant destruction (i.e. growth control rate) is as follows: 5 levels: the growth control rate is greater than or equal to 85%; 4 levels: the growth control rate is greater than or equal to 60% and less than 85%; 3 levels: the growth control rate is greater than or equal to 40% and less than 60%; 2 levels: the growth control rate is greater than or equal to 20% and less than 40%; 1 level: the growth control rate is greater than or equal to 5% and less than 20%; 0 level: the growth control rate is less than 5%. The above growth control rate is the fresh weight control rate.

[0154] Comparative Example 1 is a commercially available oxyfluorfen, which is purchased from Shanghai Macklin Biochemical Science and Technology Co., Ltd.

[0155] Table 2: Test results of herbicidal activity

[0156]

[0157]

[0158] As can be seen from Table 2, the compounds S16, S17, S18 and S19 prepared by the present application can have an inhibition rate of more than 85% on broadleaf weeds (Amaranthus retroflexus and Abutilon theophrasti) and an inhibition rate of more than 60% on grass weeds (Setaria viridis) with a small amount of addition (37.5 g a.i. / ha). The compound shown in Comparative Example 1 has an inhibition rate of only 40%-60% on Abutilon theophrasti and an inhibition rate of only 20%-40% on Setaria viridis with a small amount of addition. Therefore, the compound obtained by the present application has high herbicidal activity.

[0159] The above description is only a preferred embodiment of the present application, and it should be pointed out that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A pyrimidinedione derivative containing isoxazoline, characterized in that: The structural formula of the pyrimidinedione derivative is shown in Formula I: Wherein, R is selected from halogen, cyano, nitro, amino, C1-C6 alkyl, aromatic, oxygen-containing alkyl, unsaturated alkyl, aromatic alkyl, heteroaryl, C3-C6 cycloalkyl and heteroatom-containing hydrocarbon.

2. The isoxazoline-containing pyrimidinedione derivative according to claim 1, characterized in that: The oxygen-containing alkyl group includes C1~C6 alkoxy, carbonyl, formyl, alkylcarbonyl, alkoxycarbonyl; the unsaturated alkyl group includes C2~C6 alkenyl or C2~C6 alkynyl; the aromatic group-containing alkyl group includes aromatic alkyl or heteroaromatic alkyl; the heteroatom-containing hydrocarbon group includes haloalkyl, cyanoalkyl, haloalkenyl, haloalkynyl, alkylthio, haloalkylthio, haloalkoxy, haloalkylcarbonyl, haloalkoxycarbonyl, alkylaminoalkyl, haloalkylaminoalkyl or haloalkoxyalkyl.

3. The isoxazoline-containing pyrimidinedione derivative according to claim 1, characterized in that: One selected from the following compounds S1 to S40:

4. The method for preparing an isoxazoline-containing pyrimidinedione derivative according to any one of claims 1 to 3, characterized in that: The steps include: (1) Using 3-amino-4,4,4-trifluorobut-2-enoic acid ethyl ester and dimethylaminoformyl chloride as main raw materials, a condensation reaction is carried out to obtain 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoic acid ethyl ester; (2) ethyl 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoate, allyl 5-amino-2-chloro-4-fluorobenzoate, and acetic acid are mixed and reacted to obtain allyl 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoate; (3) Mixing 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester, potassium iodide, and potassium carbonate in a solvent for a second reaction, and performing TLC detection until the reaction is complete to obtain 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid allyl ester; (4) Allyl 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate and N-chlorosuccinimide are mixed and subjected to a third reaction. Finally, triethylamine and an oxime compound are added to carry out a fourth reaction to obtain a pyrimidinedione derivative containing isoxazoline.

5. The method for preparing an isoxazoline-containing pyrimidinedione derivative according to claim 4, wherein: In step (1), the solvent used in the condensation reaction is N,N-dimethylformamide; the raw materials for the condensation reaction also include sodium hydride; the molar ratio of the sodium hydride, ethyl 3-amino-4,4,4-trifluorobut-2-enoate and dimethylaminoformyl chloride is 1.3-1.7:1:1.2-1.

7.

6. The method for preparing an isoxazoline-containing pyrimidinedione derivative according to claim 4 or 5, wherein: In step (2), the molar ratio of ethyl 3-(3,3-dimethylureido)-4,4,4-trifluorobut-2-enoate to allyl 5-amino-2-chloro-4-fluorobenzoate is 1:1.0-1.5; the temperature of the first reaction is 30-150° C., and the time of the first reaction is 0.5-10 h.

7. The method for preparing isoxazoline-containing pyrimidinedione derivatives according to claim 6, characterized in that: In step (3), the molar ratio of 2-chloro-5-(2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzoic acid allyl ester, potassium iodide and potassium carbonate is 1:1.0~1.4:1.0~1.4; the temperature of the second reaction is 30~50°C, and the time of the second reaction is 0.5~10h.

8. The method for preparing an isoxazoline-containing pyrimidinedione derivative according to claim 5 or 7, wherein: In step (4), the amount ratio of the allyl 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate, N-chlorosuccinimide, triethylamine and oxime compound is 1:1.3-1.7:1.3-1.7:1.0-1.4; The structural formula of the oxime compound is shown in Formula II: Wherein, R is selected from halogen, cyano, nitro, amino, C1-C6 alkyl, aromatic, oxygen-containing alkyl, unsaturated alkyl, aromatic alkyl, heteroaryl, C3-C6 cycloalkyl and heteroatom-containing hydrocarbon group; The temperature of the third reaction is 20-50° C., and the time of the third reaction is 0.5-8 hours; the temperature of the fourth reaction is 20-30° C., and the time of the fourth reaction is 0.5-6 hours.

9. Use of the isoxazoline-containing pyrimidinedione derivative according to any one of claims 1 to 3 as a herbicide or a herbicide combination.

10. Use of the isoxazoline-containing pyrimidinedione derivative according to any one of claims 1 to 3 in the preparation of wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, water-emulsions, sprayable solutions, suspensions, dispersible oil suspensions, dusts, microcapsule suspensions, water-dispersible granules, water-soluble granules, granules for broadcasting and soil application, aerosols, ultra-low volume formulations or wax products.

Images