Uracil-based compounds containing carboxylic acid ester fragments, their preparation, herbicidal compositions, and uses

Abstract

The present invention relates to the field of pesticide herbicides, specifically to a uracil-based compound containing a carboxylic acid ester fragment, its preparation method, herbicidal composition and use. The uracil-based compound containing a carboxylic acid ester fragment provided by the present invention has better herbicidal activity than the conventional technology. [Formula 1] TIFF2024507475000092.tif30170

Description

[Technical field]

[0001] The present invention relates to the field of agricultural herbicides, and in particular to uracil-based compounds containing carboxylic acid ester fragments, their preparation methods, herbicidal compositions and uses. [Background technology]

[0002] Chemical herbicides are the most economical and effective means of weed control. However, long-term, continuous, and high-dose use of single-type or single-action chemical herbicides is likely to cause problems such as drug resistance and resistance changes in weeds. Developing new types of pesticides is an important means of solving the above problems.

[0003] Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) can catalyze the oxidation of protoporphyrinogen IX to protoporphyrin IX. PPO is a key enzyme in the same biosynthesis step of chlorophyll and heme. Inhibition of PPO in plants will eventually lead to the accumulation of the substrate protoporphyrin IX and leakage into the cytoplasm, resulting in cytoplasmic lipid peroxidation and plant chlorosis, and plant death. Over the past decades, PPO has been widely studied as an important target for herbicides.

[0004] Research on uracil compounds as herbicides began in the 1960s and peaked in the 1990s. In recent years, not many varieties have been developed, but some patents have been published. For example, CIBA-GEIGY Co., Ltd. disclosed the following general structure in US5183492A: [ka]

[0005] Subsequently, Syngenta succeeded in developing the compound Butafenacil (US5183492A), which was commercialized as a herbicide. This compound is used mainly in orchards, including vineyards, cotton fields, and non-agricultural land to control grass weeds, broadleaf weeds, sedges, etc., and has shown good weed control effects. [ka]

[0006] US5183492A also simultaneously disclosed the preparation of the following benzoyloxypropionic acid CK (compound 1 in the specification). [ka]

[0007] As can be seen from the above, the type of conventional uracil compound herbicides is relatively single, and there is little room for choice. The market needs new uracil herbicides with good herbicidal activity. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a new type of uracil herbicide having good herbicidal activity.

[0009] In the present invention, the technical solutions to solve the above technical problems are as follows:

[0010] A uracil-based compound containing a carboxylate fragment, the structure of which is shown by general formula (I): [ka]

[0011] In the formula: R 1 and R 2 are each selected from hydrogen or a methyl group; or R 1 and R 2forms a three-membered ring together with the carbon to which it is attached. R 3 is C 1 ~ 3 Alkoxy 1 ~ 3 Alkyl group, C 1 ~ 3 Haloalkoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Alkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Alkynoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkynoxy C 1 ~ 3 Alkyl group, C 1 ~ 3 AlkylS(O) n C 1 ~ 3 Alkyl group, C 3 ~ 6 Oxygen-containing cycloalkyl C 1 ~ 3 Alkyl group or C 3 ~ 9 The oxygen-containing cycloalkyl groups are selected from the group consisting of cycloalkyl groups. n=0, 1, or 2. R 1 is selected from hydrogen, and R 2 When is selected from a methyl group, the carbon atom attached to it may be selected from the R or S configuration, or is a mixture of the two.

[0012] A preferred compound of the present invention has the general formula (I): R 1 and R 2 are each selected from hydrogen or a methyl group; or R 1 and R 2 forms a three-membered ring together with the carbon to which it is attached. R 3 is C 1 ~ 3 Alkoxy 1 ~ 3 Alkyl group, C 1 ~ 3 Haloalkoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Alkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Alkynoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkynoxy C 1 ~ 3 Alkyl group, C 3 ~ 6 Oxygen-containing cycloalkyl C 1 ~ 3 Alkyl group or C 3 ~ 9 The oxygen-containing cycloalkyl groups are selected from the group consisting of cycloalkyl groups. R 1 is selected from hydrogen, and R 2 When is selected from a methyl group, the carbon atom attached thereto may be selected from the R or S configuration, or a mixture of the two, in which the ratio of R to S is from 1:99 to 99:1.

[0013] More preferred compounds of the present invention are those having the general formula (I): R 1 and R 2 are each selected from hydrogen or a methyl group. R 3 is C 1 ~ 3 Alkoxy 1 ~ 3 Alkyl group, C 1 ~ 3 Haloalkoxy C 1 ~ 3 Alkyl group, C2 ~ 6 Alkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkenoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Alkynoxy C 1 ~ 3 Alkyl group, C 2 ~ 6 Haloalkynoxy C 1 ~ 3 Alkyl group, C 3 ~ 6 Oxygen-containing cycloalkyl C 1 ~ 3 Alkyl group or C 3 ~ 9 The oxygen-containing cycloalkyl groups are selected from the group consisting of cycloalkyl groups. R 1 is selected from hydrogen, and R 2 When is selected from a methyl group, the carbon atom attached thereto may be selected from the R or S configuration, or a mixture of the two, in which the ratio of R to S is from 1:99 to 99:1.

[0014] Regarding the definition of the compound of general formula (I) shown above, general definitions of the terms used are summarized as follows.

[0015] Halogen: fluorine, chlorine, bromine or iodine. Alkyl: linear or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl or sec-butyl groups and isomers. Alkenyl: linear or branched alkene series, such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl further includes polyene series, such as 1,2-propadienyl and 2,4-hexadienyl. Alkynyl: linear or branched alkynes, such as ethynyl, propynyl and the different butynyl, pentynyl and hexynyl isomers. Alkynyl further includes polyynes, such as 2,4-hexadiynyl. Alkoxyalkyl: alkyl groups -O-alkyl-, such as CH 3 OCH 2 -. Haloalkoxyalkyl group: alkyl group -O-alkyl group-, in which the hydrogen atoms may be partially or completely replaced by halogen atoms. For example, ClCH 2 OCH 2 -. Alkenoxyalkyl group: an alkenyl group -O-alkyl group-, e.g. CH 2 =CHCH 2 OCH 2 CH 2 -. Haloalkenoxyalkyl group: an alkenyl group -O-alkyl group-, where O and CH 2 The hydrogen atoms in these alkenyl groups may be partially or completely replaced by halogen atoms. For example, ClCH=CHCH 2 OCH 2 CH 2 -. Alkynoxyalkyl group: an alkynyl group -O-alkyl group-, for example CH≡CCH 2 OCH 2 CH 2-, where O and CH≡C are not directly bonded. Haloalkynoxyalkyl group: an alkynyl group -O-alkyl group-, in which the hydrogen atoms in the alkynyl group may be replaced by halogen atoms. For example, ClC≡CCH 2 OCH 2 CH 2 -. Alkane S(O) n Alkyl group: alkyl group-S(O) n -alkyl group, where n=0, 1, or 2. For example, CH 3 SCH 2 CH 2 -, CH 3 SOCH 2 CH 2 -, CH 3 SO 2 CH 2 CH 2 -. Oxygen-containing cycloalkyl group: a substituted or unsubstituted cyclic oxygen-containing alkyl group, such as an oxygen-containing cyclopropyl group. Substituents include methyl, halogen, cyano, etc. Oxygen-containing cycloalkylalkyl group: a substituted or unsubstituted alkyl group having a cyclic oxygen-containing alkyl group, such as an oxygen-containing cyclobutyl group. Substituents include methyl, halogen, cyano, etc.

[0016] Some of the compounds of the present invention can be illustrated by the specific compounds shown in Table 1. However, the present invention is not limited to these compounds. [ka]

[0017] [Table 1] TIFF0007624525000006.tif240170TIFF0007624525000007.tif251170TIFF0007624525000008.tif251170TIFF0007624525000009.tif251170TIFF000 7624525000010.tif244170TIFF0007624525000011.tif251170TIFF0007624525000012.tif251170TIFF0007624525000013.tif244170TIFF0007624525 000014.tif251170TIFF0007624525000015.tif251170TIFF0007624525000016.tif251170TIFF0007624525000017.tif251170TIFF0007624525000018. tif244170TIFF0007624525000019.tif251170TIFF0007624525000020.tif251170TIFF0007624525000021.tif244170TIFF0007624525000022.tif71170

[0018] In a second aspect, the present invention provides a method for the synthesis of uracil-based compounds containing a carboxylic ester fragment, which comprises contacting an acid compound of formula (II) with a differently substituted alcohol, halogenated or sulfonated ester compound in the presence of a solvent. [ka] Here, in the general formulas (I) and (II), the relevant R 1 , R 2 and R 3 The definitions of are the same as those in claim 1.

[0019] The reaction temperature is 0 to 160° C., and preferably 20 to 120° C. The reaction time is 2 to 15 hours, and preferably 3 to 12 hours.

[0020] The solvent for the above reaction is at least one selected from dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, toluene, ortho-xylene, meta-xylene, para-xylene, n-heptane, n-octane, and n-nonane.

[0021] In the above reaction, the molar ratio of the carboxylic acid compound represented by formula (II) to the differently substituted alcohol, halogenated or sulfonate compound is 1:1-4, preferably 1:1.1-3.

[0022] Some of the compounds of general formula (I) of the present invention can be obtained directly by further esterification of intermediates 1-8. [ka]

[0023] Some of the compounds of the general formula (I) of the present invention can be obtained by directly obtaining the carboxylic acid of the general formula (II) by esterifying the intermediate 1-8, or by hydrolyzing the corresponding ester to obtain the carboxylic acid of the general formula (II). The carboxylic acid of the general formula (II) can be further prepared into the corresponding acyl chloride, and then contacted with an alcohol of different substitution to obtain some of the compounds of the general formula (I) of the present invention. The carboxylic acid of the general formula (II) can also be contacted with an alcohol of different substitution by a dehydrating agent to obtain some of the compounds of the general formula (I) of the present invention. The carboxylic acid of the general formula (II) can also be contacted with a halogenated or sulfonate compound to obtain some of the compounds of the general formula (I) of the present invention. [ka]

[0024] The reaction is carried out in a suitable solvent. Suitable solvents may be selected from benzene, toluene, xylene, acetone, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate, and the like. The reaction can be carried out with or without an alkali. When carried out in the presence of an alkali, the reaction rate can be increased. The alkali may be selected from alkali metal hydrides, such as sodium hydride, lithium hydride, or sodium amide, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate or potassium carbonate, organic alkalis, such as pyridine, 4-dimethylaminopyridine, triethylamine, N-methylpyrrole, diisopropylethylamine, and the like. When a dehydrating agent is used, for example, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N-dicyclohexylcarbodiimide, and the like can be used as the dehydrating agent. The acyl chloride may be prepared using an acylating agent such as thionyl chloride or oxalyl chloride. The reaction temperature may be from -10°C to the boiling point of a suitable solvent selected in the reaction, and is usually 0 to 100°C. The reaction time is 30 minutes to 20 hours, and usually 1 to 10 hours.

[0025] R 3 -X or R 3 -OH is either commercially available. X is a leaving group selected from chlorine, bromine, iodine, or sulfonate.

[0026] The method of the present invention may include necessary pre-treatment of the raw materials and necessary post-treatment of the reaction products. The means for carrying out the pre-treatment and post-treatment include, but are not limited to, drying, washing, beating, filtration, centrifugation, column chromatography, recrystallization, etc. Although some specific treatment means are provided in the examples section of the present invention, those skilled in the art should not understand them as limitations on the present invention.

[0027] Unless otherwise clearly noted, the definitions of the groups in the reaction schemes are the same as those in the preceding paragraphs.

[0028] In a third aspect, the present invention provides the use of a uracil compound containing a carboxylic acid ester fragment as a herbicide.

[0029] In a fourth aspect, the present invention provides a herbicidal composition comprising a compound of general formula (I) as an active ingredient, the content of the active ingredient in the composition being 0.1-99.9% by weight.

[0030] The compounds of the present invention have excellent killing activity against a wide range of economically important monocotyledonous and dicotyledonous annual harmful plants, can effectively control multiple kinds of weeds, can obtain good results at low doses, and can be used as herbicides. Therefore, the present invention further includes the use of the compounds of general formula (I) for weed control.

[0031] Thus, the present invention relates to a method for controlling undesirable plants or regulating plant growth, in which one or more compounds of the present invention are applied to plants (e.g., harmful plants such as monocotyledonous or dicotyledonous weeds or undesirable crop plants), seeds (e.g., grains, seeds, or asexually reproduced propagules such as tubers or shoots), or areas where plants are growing (e.g., cultivated areas). The compounds of the present invention can be used before planting (if appropriate, by introducing into the soil), before seedlings or after seedlings. The examples of each representative monocotyledonous or dicotyledonous weed plant group controlled by the compounds of the present invention mentioned below are intended to illustrate the present invention and are in no way limiting the present invention.

[0032] The monocotyledonous harmful genera are Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, and Nar. The genera include Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, and Sorghum.

[0033] The genera of dicotyledonous harmful plants are: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, and Sei. Genus Convolvulus, Datura, Desmodur, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Monarch Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Japanese, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, These include the genera Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, and Xanthium.

[0034] When the compounds of the invention are applied to the soil before seedlings, the growth of the seeds of harmful plants is stopped after treatment. The harmful plants remain in the growth stage at the time of application or die after a certain period of time. This allows persistent elimination of competition from harmful weeds for crop plants at a very early stage.

[0035] When the compounds of the invention are applied to green plant parts after seedlings, growth stops after treatment. Harmful plants remain in the growth stage at the time of application or die after a certain period of time. This allows persistent elimination of competition from harmful weeds for crop plants at a very early stage.

[0036] Therefore, the technical solution of the present invention includes the use of the compounds of general formula (I) for weed control.

[0037] The compounds of the general formula (I) of the present invention are also applied to the drying and / or defoliation of plants.

[0038] As described above, the present invention provides an agricultural herbicide comprising an active ingredient and an adjuvant, the active ingredient comprising at least one uracil-based compound containing the carboxylic acid ester fragment described above.

[0039] Preferably, the content of the active ingredient in the pesticide herbicide is 0.1-99.9% by weight.

[0040] In the present invention, the specific type of the adjuvant contained in the herbicide is not particularly limited, and may be, for example, various surfactants, solvents, etc. commonly used in the field of herbicides.

[0041] For example, the uracil compound containing the carboxylate fragment according to the present invention can be dissolved and diluted with a solvent for later use. The concentration after dissolving and diluting with a solvent is preferably 0.05 to 0.4 g / L. The solvent for dissolving the uracil compound containing the carboxylate fragment may contain at least one of dimethyl sulfoxide and N,N-dimethylformamide, and the dilution reagent may be water containing a commonly used additive. Preferably, a commonly used additive in herbicides in this field may be added to the solution in which the uracil compound is dissolved. The additive may be, for example, one or more of a surfactant, an emulsifier, etc.

[0042] In order to enhance the control effect of the uracil compound containing the carboxylate fragment of the present invention and to widen the scope of use, the uracil compound containing the carboxylate fragment of the present invention may be used alone or in combination with other commonly used herbicides (e.g., atrazine, fentrazamide, bromoxynil, pentoxazone, mesotrione, etc.). The ratio when used in combination is not particularly limited, and can be selected based on the ratio commonly used in this field as long as the control effect after combination is enhanced, the scope of use is widened, and safety is improved.

[0043] In the present invention, if there is a discrepancy between the name and the structural formula of a compound, the structural formula shall prevail, except for those with obvious errors in the structural formula.

[0044] The uracil compounds containing a carboxylic acid ester fragment provided by the present invention have superior herbicidal activity compared to the conventional techniques. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] The present invention will be described below with reference to the examples, but is not limited thereto. Any simple substitutions or improvements made by those skilled in the art to the present invention fall within the scope of protection of the present invention.

[0046] Example 1: Preparation of intermediate 1-8 Step 1: Preparation of intermediate 1-1 [ka] 20 g of 2-chloro-4-fluorobenzoic acid and 100 g of ethanol were placed in a 500 mL four-neck flask, stirred, and cooled to 0° C. 17.73 g of thionyl chloride was slowly added dropwise, and the entire process was maintained below 0° C. After the addition of thionyl chloride was completed, the temperature was raised to 75° C., refluxed and stirred, and reacted overnight. The reaction solution was centrifuged to obtain 23.01 g of intermediate 1-1.

[0047] Step 2: Preparation of intermediate 1-2 [ka] 67.46 g of intermediate 1-1 and 337.3 g of 1,2-dichloroethane were placed in a 1L four-neck flask and cooled to 0°C. 42.09 g of fuming nitric acid (90%) and 60.12 g of sulfuric acid (98%) were slowly added dropwise. After the addition was completed, the temperature was slowly raised to room temperature. The reaction was stirred until completion, and the reaction liquid was transferred to a separatory funnel and allowed to stand until stratified. The organic phase was removed, the inorganic phase was extracted with 1,2-dichloroethane, the acid in the organic phase was dissolved with ice water until the pH value of the aqueous phase was about 7.0, and the solvent was centrifuged to obtain 89.81 g of crude product. Five times the mass of n-hexane was added, recrystallized, and filtered. The filter cake was dried to obtain 42.45 g of intermediate 1-2.

[0048] Step 3: Preparation of intermediate 1-3 [ka] 60.84 g of intermediate 1-2, 4.87 g of Pt / C (5%), and 300 mL of ethanol were placed in a 1 L autoclave. The hydrogen gas pressure was controlled at 2 MPa and the temperature at 45°C, and the reaction was carried out for 11 hours. After filtering to remove Pt / C, the filtrate was centrifuged to obtain 52.48 g of crude intermediate 1-3.

[0049] Step 4: Preparation of intermediate 1-4 [ka] 52.48 g of the crude product of intermediate 1-3, 24.78 g of pyridine, and 262.4 g of dichloromethane were placed in a 500 mL four-neck flask and stirred at room temperature. After 5 minutes, 34.02 g of ethyl chloroformate was weighed and diluted with 68.04 g of dichloromethane, and then slowly added dropwise. The addition was completed in 1 hour. After reacting for 5 hours, the pH value was adjusted to be weakly acidic, water was added, and the mixture was extracted with dichloromethane. The organic phase was centrifuged to obtain 69.62 g of the crude product of intermediate 1-4.

[0050] Step 5: Preparation of Intermediate 1-5 [ka] 12.98 g of sodium ethoxide was dissolved in 38 g of DMF, stirred, and cooled to 5° C. in an ice bath. While in an ice bath, a solution of 3-amino-4,4,4-trifluorocrotonate ethyl (27.95 g) in DMF (28 g) was added dropwise. After the addition was completed, a DMF solution of 36.84 g of intermediate 1-4 was added dropwise, and the temperature was raised to 100° C. and stirred for 5 hours. After the reaction was completed, the pH was adjusted to be acidic, and the organic phase was extracted with ethyl acetate, washed with saturated saline, dried with anhydrous sodium sulfate, and the solvent was centrifuged to obtain 50 g of a crude product. The mixture was purified by column chromatography to obtain 19.05 g of intermediate 1-5.

[0051] Step 6: Preparation of Intermediate 1-6 [ka] 19.05 g of intermediate 1-5 and 8.287 g of anhydrous potassium carbonate were placed in a one-neck flask, dissolved in 60 g of THF, and 7.566 g of dimethyl sulfate were added and stirred at room temperature overnight. After the reaction was completed, the THF was centrifuged, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the organic phase was centrifuged to obtain 19.62 g of crude intermediate 1-6.

[0052] Step 7: Preparation of Intermediate 1-7 [ka] At room temperature, 19.62 g of intermediate 1-6 was dissolved in 150 mL of glacial acetic acid, and the same volume of 36% hydrochloric acid was added and refluxed for 8 hours. After the reaction was completed, the excess solvent was removed by vacuum distillation, and the residue was added with water to precipitate a solid, which was stirred and filtered. The filter cake was eluted with water three times and dried at 60°C to obtain 12.73 g of crude intermediate 1-7.

[0053] Step 8: Preparation of Intermediate 1-8 [ka] 6.8 g of intermediate 1-7, 35 g of 1,2-dichloroethane, 1 drop of DMF, and 3.316 g of thionyl chloride were placed in a 100 ml one-neck flask and refluxed for 3 hours. After the reaction was completed, the excess thionyl chloride and the solvent were centrifuged to obtain 6.22 g of crude intermediate 1-8.

[0054] Example 2: Preparation of Compound 3 Step 1: Preparation of Intermediate 3-1 [ka] The intermediate 1-8 (1 g) and 320 mg of methyl glycolate in Example 1 were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 394 mg of triethylamine was added dropwise. After the addition was completed, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 1.02 g of intermediate 3-1.

[0055] Step 2: Preparation of intermediate 3-2 [ka] 1.02 g of intermediate 3-1, 6.12 g of hydrochloric acid (36%), and 6.12 g of acetic acid were placed in a reaction flask and refluxed for 40 minutes. The reaction solution was centrifuged to obtain 1.01 g of intermediate 3-2.

[0056] Step 3: Preparation of intermediate 3-3 [ka] 1.01 g of intermediate 3-2, 340 mg of thionyl chloride, 2 drops of DMF, and 5.5 g of dichloroethane were placed in a reaction flask and refluxed for 3 hours. The reaction solution was centrifuged to obtain 1.02 g of intermediate 3-3.

[0057] Step 4: Preparation of compound 3 [ka] 103.29 mg of 2-methoxyethanol and 228.95 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 3-3 (0.50 g) produced in step 3 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 165 mg of compound 3. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.16 (d, J = 7.8 Hz, 1H), 7.95 (d, J = 9.6 Hz, 1H), 6.62 (s, 1H), 4.99 (s, 2H), 4.30 - 4.23 (m, 2H), 3.59 - 3.52 (m, 2H), 3.42 (s, 3H), 3.26 (s, 3H). LCMS (ESI) [M + H] + =483.05, Found =482.61.

[0058] Example 3: Preparation of Compound 10 Step 1: Preparation of compound 10 [ka] 99.83 mg of 2-(allyloxy)ethanol and 123.60 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 2.5 mL of a dichloromethane solution of intermediate 3-3 (0.40 g) in Example 2 was added dropwise. After the addition was completed, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the product was purified by column chromatography to obtain 260 mg of a pale yellow oily product, compound 10. 1 H NMR (400 MHz, DMSO-d6) δ 8.16 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.61 (s, 1H), 5.93 - 5.72 (m, 1H), 5.24 (dq, J = 17.4, 1.8 Hz, 1H), 5.13 (dt, J = 10.1, 1.6 Hz, 1H), 4.99 (s, 2H), 4.27 (dd, J = 5.6, 3.6 Hz, 2H), 3.96 (dt, J = 5.4, 1.6 Hz, 2H), 3.67 - 3.55 (m, 2H). LCMS (ESI) [M + H] + =509.07, Found =508.62.

[0059] Example 4: Preparation of Compound 28 Step 1: Preparation of compound 28 [ka] 95.70 mg of 2-(propargyloxy)ethanol and 148.82 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 3-3 (0.50 g) in Example 2 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the product was purified by column chromatography to obtain 110 mg of a pale yellow oily product, compound 28. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.15 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.61 (s, 1H), 4.98 (s, 2H), 4.27 (dd, J = 5.7, 3.4 Hz, 2H), 4.16 (d, e = 2.4 Hz, 2H), 3.75 - 3.63 (m, 2H), 3.43 (d, J = 11.5 Hz, 4H). LCMS (ESI) [M + H] + =507.05, Found =506.83.

[0060] Example 5: Preparation of intermediate 54-3 Step 1: Preparation of intermediate 54-1 [ka] 20 g of intermediate 1-8 in Example 1, 4.86 g of D-methyl lactate, and 100 g of dichloromethane were placed in a reaction flask, and nitrogen gas was blown in and stirred at room temperature. Within 60 minutes, 5.9 g of triethylamine was added dropwise, and when the addition was completed, the mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was purified by column chromatography to obtain 16 g of intermediate 54-1.

[0061] Step 2: Preparation of intermediate 54-2 [ka] 15 g of intermediate 54-1, 90 g of hydrochloric acid (36%), and 90 g of acetic acid were added to a reaction flask and stirred at 60° C. for 40 minutes to complete the reaction. The solvent was centrifuged to obtain 14 g of intermediate 54-2.

[0062] Step 3: Preparation of intermediate 54-3 [ka] 5.0 g of intermediate 54-2, 1.63 g of thionyl chloride, 25 g of 1,2-dichloroethane, and 2 drops of DMF were placed in a reaction flask and stirred under reflux at 90° C. The reaction was completed in 1 hour. The solvent was centrifuged to obtain 5.1 g of intermediate 54-3.

[0063] Example 6: Preparation of Compound 54 [ka] 0.6g of intermediate 54-3 in Example 5, 0.120g of 2-methoxyethanol, 10g of dichloromethane, and 0.2g of triethylamine were added to a reaction flask, and nitrogen gas was blown in and the mixture was stirred at room temperature for 1 hour to complete the reaction. After the reaction was completed, the mixture was purified by column chromatography to obtain 0.350g of compound 54. 1 H NMR (400 MHz, CDCl 3 ) δ 7.97 (dd, J = 7.7, 2.0 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J = 7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J = 4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s, 3H), 1.62 (d, J = 7.1 Hz, 3H). LCMS (ESI) [M + H] + =497.07, Found =497.16.

[0064] Example 7: Preparation of Compound 61 Step 1: Preparation of compound 61 [ka] 290 mg of 2-(allyloxy)ethanol and 330 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 10 mL of a dichloromethane solution of intermediate 54-3 (1.0 g) in Example 5 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 800 mg of compound 61. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.14 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.62 (d, J = 3.0 Hz, 1H), 5.84 (ddtd, J = 16.9, 10.6, 5.3, 1.1 Hz, 1H), 5.31 (qt, J = 6.5, 3.3 Hz, 1H), 5.26 5.20 (m, 1H), 5.12 (dq, J = 10.4, 1.6 Hz, 1H), 4.34 4.20 (m, 2H), 3.95 (dt, J = 5.3, 1.5 Hz, 2H), 3.60 (ddd, J = 6.0, 4.2, 1.4 Hz, 2H), 3.45 3.40 (m, 3H), 1.53 (d, J = 7.0 Hz, 3H).LCMS (ESI) [M + H] + =523.08, Found =522.96.

[0065] Example 8: Preparation of Compound 79 Step 1: Preparation of compound 79 [ka] 1g of intermediate 54-3 described in Example 5 was dissolved in 5mL of 1,2-dichloroethane, and a solution of propynol ethoxylate (220mg) in 1,2-dichloroethane was added dropwise, stirred at 20°C for 10 minutes, and then 330mg of triethylamine was added dropwise. The raw material was detected to have reacted completely by LCMS, and 20mL of hydrochloric acid (1N) was added, washed, and separated. The organic phase was dried over anhydrous sodium sulfate and purified by chromatography to obtain 200mg of compound 79, a colorless oily liquid. 1 H NMR (400 MHz, Chloroform-d) δ 7.97 (dd, J = 7.7, 2.1 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.38 (d, J = 1.0 Hz, 1H), 5.36 (q, J = 7.1 Hz, 1H), 5.30 (s, 1H), 4.17 (dd, J = 2.4, 0.7 Hz, 2H), 3.76 (dt, J = 6.9, 3.0 Hz, 2H), 3.59 - 3.55 (m, 3H), 1.62 (dd, J = 7.1, 1.0 Hz, 3H), 1.33 - 1.23 (m, 2H). .LCMS (ESI) [M + H] + =521.07, Found =521.21.

[0066] Example 9: Preparation of Compound 88 Step 1: Preparation of Compound 88 [ka] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 54-3 (0.60 g) in Example 5 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 545 mg of a colorless oily product, compound 88. 1 H NMR (400 MHz, DMSO-d 6) δ 8.15 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.63 (d, J = 2.9 Hz, 1H), 5.32 (dd, J = 7.0, 2.0 Hz, 1H), 4.39 - 4.21 (m, 2H), 3.42 (s, 3H), 2.83 - 2.66 (m, 2H), 2.11 - 2.07 (m, 3H), 1.55 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =512.04, Found =512.54.

[0067] Example 10: Preparation of Compound 92 Step 1: Preparation of Compound 92 [ka] 250.0 mg of compound 88 and 10 mL of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 84.11 mg of m-chloroperbenzoic acid was added. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the product was purified by column chromatography to obtain 177 mg of a colorless oil, compound 92. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.22 (d, J = 7.7 Hz, 1H), 8.01 (d, J = 9.6 Hz, 1H), 6.70 (d, J = 2.9 Hz, 1H), 5.45 - 5.35 (m, 1H), 4.66 - 4.42 (m, 2H), 3.49 (s, 3H), 3.29 - 3.02 (m, 2H), 2.73 - 2.62 (m, 3H), 1.61 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =529.04, Found =528.65.

[0068] Example 11: Preparation of Compound 93 Step 1: Preparation of compound 93 [ka] 97.77 mg of 2-methylsulfonylethanol and 99.61 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 2 mL of a dichloromethane solution of intermediate 54-3 (0.30 g) in Example 5 was added dropwise. After the addition was completed, the reaction was carried out at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 192 mg of compound 93. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.16 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 9.5 Hz, 1H), 6.63 (d, J = 3.2 Hz, 1H), 5.44 - 5.28 (m, 1H), 4.57 - 4.41 (m, 2H), 3.55 (t, J = 5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =545.03, Found =544.58

[0069] Example 12: Preparation of Compound 96 [ka] In a 25 mL one-neck flask, 0.5 g of intermediate 54-3 in Example 5, 5 mL of dichloromethane, 97.2 mg of (S)-glycidol, and 0.17 g of triethylamine were added and stirred at room temperature overnight. After the reaction was completed, 5 mL of water was added, stirred, and separated to obtain an organic phase, which was dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The mixture was purified by column chromatography to obtain 215 mg of compound 96. 1 H NMR (400 MHz, CDCl 3) δ 7.97 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 9.1 Hz, 1H), 6.38 (d, J = 1.1 Hz, 1H), 5.37 (q, J = 7.0 Hz, 1H), 4.49 (dd, J = 12.2, 3.0 Hz, 1H), 4.07 - 3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J = 9.8, 4.9 Hz, 1H), 2.84 (q, J = 4.4 Hz, 1H), 2.63 (dd, J = 4.7, 2.6 Hz, 1H), 1.62 (t, J = 9.2 Hz, 3H). LCMS (ESI) [M + H] + =495.05, Found =495.05.

[0070] Example 13: Preparation of Compound 97 [ka] In a 25 mL one-neck flask, 0.5 g of intermediate 54-3 in Example 5, 5 mL of dichloromethane, 97.2 mg of (R)-glycidol, and 0.17 g of triethylamine were added and stirred at room temperature overnight. After the reaction was completed, 5 mL of water was added, stirred, and separated to obtain an organic phase, which was dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The mixture was purified by column chromatography to obtain 330 mg of compound 97. 1 H NMR (400 MHz, CDCl 3) δ 7.97 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.37 (d, J = 2.3 Hz, 1H), 5.37 (qd, J = 7.1, 2.2 Hz, 1H), 4.49 (dd, J = 12.2, 2.2 Hz, 1H), 4.13 - 3.98 (m, 1H), 3.57 (d, J = 2.0 Hz, 3H), 3.20 (tt, J = 5.7, 2.8 Hz, 1H), 2.84 (t, J = 4.5 Hz, 1H), 2.67 (dt, J = 10.9, 5.6 Hz, 1H), 1.63 (d, J = 7.1 Hz, 3H). LCMS (ESI) [M + H] + =495.05, Found =495.30.

[0071] Example 14: Preparation of intermediate 105-3 Step 1: Preparation of Intermediate 105-1 [ka] 324.4 mg of L-methyl lactate was placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and the intermediate 1-8 (1 g) in Example 1 was added dropwise, followed by 394 mg of triethylamine. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 923 mg of intermediate 105-1.

[0072] Step 2: Preparation of intermediate 105-2 [ka] 923 mg of intermediate 105-1, 6.46 g of hydrochloric acid (36%), and 6.46 g of acetic acid were placed in a reaction flask and refluxed for 40 minutes. The reaction solution was centrifuged to obtain 900 g of intermediate 105-2.

[0073] Step 3: Preparation of intermediate 105-3 [ka] 900 mg of intermediate 105-2, 366.49 mg of thionyl chloride, 2 drops of DMF, and 4.5 g of 1,2-dichloroethane were placed in a reaction flask and refluxed for 3 hours. The reaction solution was centrifuged to obtain 800 mg of intermediate 105-3.

[0074] Example 15: Preparation of Compound 105 [ka] 0.6g of intermediate 105-3 in Example 14, 0.120g of 2-methoxyethanol, 10g of dichloromethane, and 0.2g of triethylamine were added to a reaction flask, and nitrogen gas was blown in and the mixture was stirred at room temperature for 1 hour to complete the reaction. The mixture was purified by column chromatography to obtain 0.40g of compound 105. 1 H NMR (400 MHz, CDCl 3 ) δ 7.97 (dd, J = 7.7, 2.0 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J = 7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J = 4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s, 3H), 1.62 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =497.07, Found =497.34.

[0075] Example 16: Preparation of Compound 112 [ka] The intermediate 105-3 (1 g) in Example 14 was weighed and placed in a 25 ml one-neck flask, and 10 mL of dichloromethane, 268 mg of 2-allyloxyethanol, and 330 mg of triethylamine were added and stirred at room temperature to react. After 15 hours, the reaction was detected to be complete by LCMS. 5 mL of water was added, stirred, and separated to obtain an organic phase. The organic phase was dried and excess solvent was removed by distillation under reduced pressure. The product was purified by column chromatography (PE:EA=4:1) to obtain 768 mg of compound 112, a colorless oily liquid. 1 H NMR (400 MHz, CDCl 3 ) δ 7.97 (dd, J = 7.7, 1.9 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.37 (s, 1H), 5.87 (ddd, J = 22.7, 10.7, 5.6 Hz, 1H), 5.35 (t, J = 7.0 Hz, 1H), 5.27 (dd, J = 17.2, 1.5 Hz, 1H), 5.18 (d, J = 10.4 Hz, 1H), 4.43 - 4.24 (m, 2H), 4.00 (d, J = 5.4 Hz, 2H), 3.65 (t, J = 4.8 Hz, 2H), 3.57 (s, 3H), 1.62 (d, J = 7.1 Hz, 3H). LCMS (ESI) [M + H] + =523.08, Found =523.10

[0076] Example 17: Preparation of Compound 130 [ka] 1g of intermediate 105-3 in Example 14, 5 mL of 1,2-dichloroethane, and a solution of propynol ethoxylate (220 mg) in 1,2-dichloroethane were stirred at 20° C. for 10 minutes, and then 330 mg of triethylamine was added dropwise. The raw material was detected to have reacted completely by LCMS, and 20 mL of hydrochloric acid (1N) was added, washed, and separated. The organic phase was dried over anhydrous sodium sulfate and purified by chromatography to obtain 230 mg of compound 130, a colorless oily liquid. 1 H NMR (400 MHz, Chloroform-d) δ 7.97 (dd, J = 7.7, 2.1 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.38 (d, J = 1.0 Hz, 1H), 5.36 (q, J = 7.1 Hz, 1H), 5.30 (s, 1H), 4.17 (dd, J = 2.4, 0.7 Hz, 2H), 3.76 (dt, J = 6.9, 3.0 Hz, 2H), 3.59 - 3.55 (m, 3H), 1.62 (dd, J = 7.1, 1.0 Hz, 3H), 1.33 - 1.23 (m, 2H). .LCMS (ESI) [M + H] + =521.07, Found =521.12.

[0077] Example 18: Preparation of Compound 139 Step 1: Preparation of Compound 139 [ka] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 105-3 (0.60 g) in Example 14 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 419 mg of a colorless oily product, compound 139. 1 H NMR (400 MHz, DMSO-d 6) δ 8.15 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.63 (d, J = 2.9 Hz, 1H), 5.32 (dd, J = 7.0, 2.0 Hz, 1H), 4.39 - 4.21 (m, 2H), 3.42 (s, 3H), 2.83 - 2.66 (m, 2H), 2.11 - 2.07 (m, 3H), 1.55 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =512.04, Found =512.54.

[0078] Example 19: Preparation of Compound 143 Step 1: Preparation of compound 143 [ka] 250.0 mg of compound 139 in Example 18 and 10 mL of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 84.11 mg of m-chloroperbenzoic acid was added. After the dropwise addition was completed, the mixture was reacted at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 170 mg of a colorless oily product, compound 143. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.21 (d, J = 7.7 Hz, 1H), 8.01 (d, J = 9.6 Hz, 1H), 6.70 (d, J = 2.8 Hz, 1H), 5.41 (qt, J = 7.2, 1.6 Hz, 1H), 4.70 - 4.43 (m, 2H), 3.48 (s, 3H), 3.27 - 3.00 (m, 2H), 2.65 (d, J = 2.6 Hz, 3H), 1.61 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =529.04, Found =528.65.

[0079] Example 20: Preparation of Compound 144 Step 1: Preparation of compound 144 [ka] 97.77 mg of 2-methylsulfonylethanol and 99.61 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 2 mL of a dichloromethane solution of intermediate 105-3 (0.30 g) in Example 14 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 166 mg of compound 144. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.16 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 9.5 Hz, 1H), 6.63 (d, J = 3.2 Hz, 1H), 5.43 - 5.32 (m, 1H), 4.57 - 4.41 (m, 2H), 3.55 (t, J = 5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H). LCMS (ESI) [M + H] + =545.03, Found =544.58.

[0080] Example 21: Preparation of Compound 147 [ka] In a 25 mL one-neck flask, 0.5 g of intermediate 105-3 in Example 14, 5 mL of dichloromethane, 97.2 mg (S)-glycidol, and 0.17 g of triethylamine were added and stirred at room temperature overnight. After the reaction was completed, 5 mL of water was added, stirred, and separated to obtain an organic phase, which was dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The mixture was purified by column chromatography to obtain 215 mg of compound 147. 1 H NMR (400 MHz, CDCl 3) δ 7.97 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 9.1 Hz, 1H), 6.38 (d, J = 1.1 Hz, 1H), 5.37 (q, J = 7.0 Hz, 1H), 4.49 (dd, J = 12.2, 3.0 Hz, 1H), 4.07 - 3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J = 9.8, 4.9 Hz, 1H), 2.84 (q, J = 4.4 Hz, 1H), 2.63 (dd, J = 4.7, 2.6 Hz, 1H), 1.62 (t, J = 9.2 Hz, 3H). LCMS (ESI) [M + H] + =495.05, Found =495.12.

[0081] Example 22: Preparation of Compound 148 [ka] In a 25 mL one-neck flask, 0.5 g of intermediate 105-3 in Example 14, 5 mL of dichloromethane, 97.2 mg of (R)-glycidol, and 0.17 g of triethylamine were added and stirred at room temperature overnight. After the reaction was completed, 5 mL of water was added, stirred, and separated to obtain an organic phase, which was dried over anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure. The mixture was purified by column chromatography to obtain 240 mg of compound 148. 1 H NMR (400 MHz, CDCl 3) δ 7.97 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 9.1 Hz, 1H), 6.37 (d, J = 2.2 Hz, 1H), 5.37 (dd, J = 7.1, 2.1 Hz, 1H), 4.49 (dd, J = 12.2, 2.3 Hz, 1H), 4.07 (ddd, J = 12.2, 5.9, 2.0 Hz, 1H), 3.57 (d, J = 1.9 Hz, 3H), 3.20 (tt, J = 5.8, 2.8 Hz, 1H), 2.83 (t, J = 4.5 Hz, 1H), 2.72 - 2.62 (m, 1H), 1.63 (d, J = 7.1 Hz, 3H). LCMS (ESI) [M + H] + =495.05, Found =495.06.

[0082] Example 23: Preparation of intermediate 156-3 Step 1: Preparation of intermediate 156-1 [ka] 20.0 g of intermediate 1-8 in Example 1, 4.86 g of methyl lactate, and 100 g of dichloromethane were placed in a reaction flask, and nitrogen gas was blown in and stirred at room temperature. Within 60 minutes, 5.9 g of triethylamine was added dropwise, and when the addition was completed, the mixture was stirred at room temperature overnight. After the reaction was completed, the mixture was purified by column chromatography to obtain 15.8 g of intermediate 156-1.

[0083] Step 2: Preparation of intermediate 156-2 [ka] 15 g of intermediate 22-1, 90 g of hydrochloric acid (36%), and 90 g of acetic acid were added to a reaction flask and stirred at 60° C. for 40 minutes to complete the reaction. The solvent was centrifuged to obtain 13.7 g of intermediate 156-2.

[0084] Step 3: Preparation of intermediate 156-3 [ka] 900 mg of intermediate 156-2, 366.49 mg of thionyl chloride, 2 drops of DMF, and 4.5 g of 1,2-dichloroethane were placed in a reaction flask and refluxed for 3 hours. The reaction solution was centrifuged to obtain 820 mg of intermediate 156-3.

[0085] Example 24: Preparation of Compound 156 [ka] 0.6g of intermediate 156-3 in Example 23, 0.120g of 2-methoxyethanol, 10g of dichloromethane, and 0.2g of triethylamine were added to a reaction flask, and nitrogen gas was blown in and the mixture was stirred at room temperature for 1 hour to complete the reaction. After the reaction was completed, the mixture was purified by column chromatography to obtain 0.395g of compound 156. 1 H NMR (400 MHz, CDCl 3 ) δ 7.97 (dd, J = 7.7, 2.0 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J = 7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J = 4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s,, 3H), 1.62 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =497.07, Found =497.30.

[0086] Example 25: Preparation of Compound 163 [ka] Compound 163 was prepared by using the intermediate 156-3 in Example 23 and 2-(allyloxy)ethanol according to the methods of Examples 7 and 16.

[0087] Example 26: Preparation of Compound 181 [ka] Compound 181 was prepared by using the intermediate 156-3 in Example 23 and propynol ethoxylate according to the methods of Example 8 and Example 17. 1 H NMR (400 MHz, Chloroform-d) δ 7.97 (dd, J = 7.7, 2.1 Hz, 1H), 7.40 (d, J = 9.2 Hz, 1H), 6.38 (d, J = 1.0 Hz, 1H), 5.36 (q, J = 7.1 Hz, 1H), 5.30 (s, 1H), 4.17 (dd, J = 2.4, 0.7 Hz, 2H), 3.76 (dt, J = 6.9, 3.0 Hz, 2H), 3.59 - 3.55 (m, 3H), 1.62 (dd, J = 7.1, 1.0 Hz, 3H), 1.33 - 1.23 (m, 2H). .LCMS (ESI) [M + H] + =521.07, Found =521.11.

[0088] Example 27: Preparation of Compound 190 Step 1: Preparation of Compound 190 [ka] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 156-3 (0.60 g) in Example 23 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 409 mg of a colorless oily product, compound 190. 1 H NMR (400 MHz, DMSO-d 6) δ 8.15 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.63 (d, J = 2.9 Hz, 1H), 5.32 (dd, J = 7.0, 2.0 Hz, 1H), 4.39 - 4.21 (m, 2H), 3.42 (s, 3H), 2.83 - 2.66 (m, 2H), 2.11 - 2.07 (m, 3H), 1.55 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =512.04, Found =512.54.

[0089] Example 28: Preparation of Compound 194 Step 1: Preparation of Compound 194 [ka] 250.0 mg of compound 190 and 10 mL of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 84.11 mg of m-chloroperbenzoic acid was added. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the product was purified by column chromatography to obtain 166 mg of a colorless oil, compound 194. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.21 (d, J = 7.7 Hz, 1H), 8.01 (d, J = 9.6 Hz, 1H), 6.70 (d, J = 2.8 Hz, 1H), 5.41 (qt, J = 7.2, 1.6 Hz, 1H), 4.70 - 4.43 (m, 2H), 3.48 (s, 3H), 3.27 - 3.00 (m, 2H), 2.65 (d, J = 2.6 Hz, 3H), 1.61 (d, J = 7.0 Hz, 3H). LCMS (ESI) [M + H] + =529.04, Found =528.65.

[0090] Example 29: Preparation of Compound 195 Step 1: Preparation of Compound 195 [ka] 97.77 mg of 2-methylsulfonylethanol and 99.61 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 2 mL of a dichloromethane solution of intermediate 156-3 (0.30 g) in Example 23 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 168 mg of compound 195. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.16 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 9.5 Hz, 1H), 6.63 (d, J = 3.2 Hz, 1H), 5.43 - 5.32 (m, 1H), 4.57 - 4.41 (m, 2H), 3.55 (t, J = 5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J = 7.2 Hz, 3H). LCMS (ESI) [M + H] + =545.03, Found =544.58.

[0091] Example 30: Preparation of Compound 198 [ka] Compound 198 was prepared by using the intermediate 156-3 in Example 23 and (S)-glycidol according to the methods of Examples 12 and 21. 1 H NMR (400 MHz, CDCl 3) δ 7.97 (d, J = 7.7 Hz, 1H), 7.40 (d, J = 9.1 Hz, 1H), 6.38 (d, J = 1.1 Hz, 1H), 5.37 (q, J = 7.0 Hz, 1H), 4.49 (dd, J = 12.2, 3.0 Hz, 1H), 4.07 - 3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J = 9.8, 4.9 Hz, 1H), 2.84 (q, J = 4.4 Hz, 1H), 2.63 (dd, J = 4.7, 2.6 Hz, 1H), 1.62 (t, J = 9.2 Hz, 3H). LCMS (ESI) [M + H] + =495.05, Found =495.04.

[0092] Example 31: Preparation of Compound 199

Chemical Structure

[0093] Example 32: Preparation of Compound 207 Step 1: Preparation of intermediate 207-1 [ka] 2.36 g of methyl 2-hydroxyisobutyrate, 1.91 g of DMAP, and 50 g of dichloromethane were added to a reaction flask, and nitrogen gas was blown into the flask and stirred at room temperature. Within 20 minutes, 5 g of intermediate 1-8 in Example 1 was added dropwise, and after the addition was completed, the mixture was stirred at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 3.57 g of intermediate 207-1.

[0094] Step 2: Preparation of intermediate 207-2 [ka] 3.57 g of intermediate 207-1, 20 g of hydrochloric acid (36%), and 20 g of acetic acid were placed in a reaction flask and stirred at 120° C. for 2 hours to complete the reaction. The reaction solution was placed in 100 ml of ice water, extracted with EA, and the organic phase was centrifuged to obtain 2.78 g of intermediate 207-2.

[0095] Step 3: Preparation of compound 207-3 [ka] 2.78 g of intermediate 207-2, 1.1 g of thionyl chloride, 30 g of 1,2-dichloroethane, and 2 drops of DMF were added to a reaction flask and stirred under reflux at 90° C. The reaction was completed in 1 hour. The solvent was centrifuged to obtain 3.2 g of intermediate 207-3.

[0096] Step 4: Preparation of Compound 207 [ka] 103.29 mg of 2-methoxyethanol and 228.95 mg of triethylamine were placed in a reaction flask, cooled in an ice bath, stirred, and nitrogen gas was blown in, and 3 mL of a dichloromethane solution of intermediate 3-3 (0.50 g) produced in step 5 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours. The organic phase was dried and excess solvent was removed by distillation under reduced pressure. The product was purified by column chromatography to obtain 120 mg of a white solid, compound 207. 1 H NMR (400 MHz, CDCl 3 ) δ 7.86 (d, J = 7.7 Hz, 1H), 7.38 (d, J = 9.2 Hz, 1H), 6.38 (s, 1H), 4.50 - 4.18 (m, 2H), 3.59 (s, 2H), 3.57 (s, 3H), 3.32 (s, 3H), 1.69 (s, 6H). LCMS (ESI) [M + H] + = 511.08, Found = 511.12.

[0097] Example 33: Preparation of Compound 214 Step 1: Preparation of compound 214 [ka] 1.04 g of 2-(allyloxy)ethanol, 1.24 g of DMAP, and 30 g of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, and nitrogen gas was blown in, and a 20 mL dichloromethane solution of intermediate 207-3 (3.2 g) in Example 32 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 600 mg of compound 214. 1 H NMR (400 MHz, DMSO-d 6) δ 8.07 (d, J = 7.8 Hz, 1H), 7.92 (d, J = 9.6 Hz, 1H), 6.63 (s, 1H), 5.90 - 5.73 (m, 1H), 5.25 - 5.08 (m, 2H), 4.27 - 4.19 (m, 2H), 3.91 (dt, J = 5.3, 1.6 Hz, 2H), 3.59 - 3.55 (m, 2H), 3.42 (d, J = 1.3 Hz, 3H), 1.63 (s, 6H).LCMS (ESI) [M + H] + =537.10, Found =536.98.

[0098] Example 34: Preparation of Compound 249 [ka] 0.71 g of (S)-glycidol, 0.5 g of DMAP, 2 g of triethylamine, and 2 mL of dichloromethane were placed in a reaction flask, cooled in an ice bath, nitrogen gas was blown in, and a solution of 2.57 g of the intermediate 207-3 in Example 32 in 20 mL of dichloromethane was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 3 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 3g of an oily compound, compound 249. 1 H NMR (400 MHz, Chloroform-d) δ 7.87 (d, J = 7.6 Hz, 1H), 7.39 (d, J = 9.1 Hz, 1H), 6.38 (s, 1H), 4.45 (dd, J = 12.2, 3.4 Hz, 1H), 4.04 (dd, J = 12.2, 6.0 Hz, 1H), 3.57 (s, 3H), 3.21 (dq, J = 6.4, 3.3 Hz, 1H), 2.83 (t, J = 4.5 Hz, 1H), 2.64 (dd, J = 4.9, 2.6 Hz, 1H), 1.70 (s, 6H).LCMS (ESI) [M + H] + =509.07, Found =508.93.

[0099] Example 35: Preparation of Compound 250 [ka] 0.71 g of (R)-glycidol, 0.5 g of DMAP, 2 g of triethylamine, and 2 mL of dichloromethane were placed in a reaction flask, cooled in an ice bath, nitrogen gas was blown in, and 2.57 g of a solution of intermediate 207-3 in Example 32 in 20 mL of dichloromethane was added dropwise. After the addition was completed, the reaction was carried out at room temperature for 3 hours. After the reaction was completed, the mixture was purified by column chromatography to obtain 2.9 g of an oily compound, compound 250. 1 H NMR (400 MHz, Chloroform-d) δ 7.87 (d, J = 7.7 Hz, 1H), 7.39 (d, J = 9.2 Hz, 1H), 6.38 (s, 1H), 4.44 (dd, J = 12.2, 3.4 Hz, 1H), 4.04 (dd, J = 12.2, 6.0 Hz, 1H), 3.56 (s, 3H), 3.20 (dq, J = 6.1, 3.5 Hz, 1H), 2.82 (t, J = 4.5 Hz, 1H), 2.63 (dd, J = 4.8, 2.6 Hz, 1H), 1.70 (s, 6H).LCMS (ESI) [M + H] + =509.07, Found =509.10.

[0100] Example 36: Preparation of Compound 251 Step 1: Preparation of Compound 251 [ka] Compound 251 was prepared by using the intermediate 207-3 in Example 32 and (±)-glycidol according to the methods of Example 34 and Example 35. 1H NMR (400 MHz, Chloroform-d) δ 7.87 (d, J = 7.6 Hz, 1H), 7.39 (d, J = 9.1 Hz, 1H), 6.38 (s, 1H), 4.45 (dd, J = 12.2, 3.4 Hz, 1H), 4.04 (dd, J = 12.2, 6.0 Hz, 1H), 3.57 (s, 3H), 3.21 (dq, J = 6.4, 3.3 Hz, 1H), 2.83 (t, J = 4.5 Hz, 1H), 2.64 (dd, J = 4.9, 2.6 Hz, 1H), 1.70 (s, 6H).LCMS (ESI) [M + H] + =509.07, Found =508.97.

[0101] Example 37: Preparation of Compound 258 Step 1: Preparation of compound 258-1 [ka] 0.6 g of methyl 1-hydroxy-1-cyclopropanecarboxylate, 0.57 g of DMAP, and 25 g of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 10 mL of a dichloromethane solution of intermediate 1-8 (1.22 g) in Example 1 was added dropwise. After the addition was completed, the reaction was carried out at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 1.1 g of intermediate 258-1.

[0102] Step 2: Preparation of intermediate 258-2 [ka] 1.1 g of intermediate 258-1, 8 g of hydrochloric acid (36%), and 8 g of acetic acid were placed in a reaction flask and stirred at 110° C. for 4 hours to complete the reaction. The reaction solution was placed in 100 ml of ice water, extracted with EA, and the organic phase was centrifuged to obtain 1.06 g of intermediate 258-2.

[0103] Step 3: Preparation of compound 258-3 [ka] 1.06 g of intermediate 258-2, 0.42 g of thionyl chloride, 20 g of 1,2-dichloroethane, and 2 drops of DMF were added to a reaction flask and stirred under reflux at 90° C. The reaction was completed in 1 hour. The solvent was centrifuged to obtain 1.1 g of intermediate 258-3.

[0104] Step 4: Preparation of Compound 258 [ka] 0.211 g of 2-methoxyethanol, 0.323 g of triethylamine, and 15 g of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 10 mL of a dichloromethane solution of intermediate 258-3 (1.0 g) was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 201 mg of compound 258. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.21 (d, J = 7.6 Hz, 1H), 8.01 (d, J = 9.4 Hz, 1H), 6.70 (s, 1H), 4.29 (t, J = 4.7 Hz, 2H), 3.57 (t, J = 4.6 Hz, 2H), 3.49 (s, 3H), 3.29 (s, 3H), 1.67-1.48 (m, 4H).LCMS (ESI) [M + H] + =509.07, Found =508.92.

[0105] Example 38: Preparation of Compound 300 Step 1: Preparation of Compound 300 [ka] 0.308 g of (S)-glycidol, 0.485 g of triethylamine, and 20 g of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, and nitrogen gas was blown in, and a 15 mL dichloromethane solution of intermediate 258-3 (1.5 g) in Example 37 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 212 mg of compound 300. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.22 (d, J = 7.8 Hz, 1H), 8.01 (d, J = 9.6 Hz, 1H), 6.69 (s, 1H), 4.52 (dd, J = 12.3, 2.6 Hz, 1H), 4.03 (dd, J = 12.3, 6.3 Hz, 1H), 3.51 - 3.45 (m, 3H), 3.24 (ddt, J = 6.7, 4.2, 2.6 Hz, 1H), 2.83 (dd, J = 5.0, 4.2 Hz, 1H), 2.68 (dd, J = 5.0, 2.6 Hz, 1H), 1.68 - 1.51 (m, 4H).LCMS (ESI) [M + H] + =507.05, Found =506.96.

[0106] Example 39: Preparation of Compound 301 Step 1: Preparation of Compound 301 [ka] 0.205 g of (R)-glycidol, 0.323 g of triethylamine, and 15 g of dichloromethane were placed in a reaction flask, cooled in an ice bath, stirred, nitrogen gas was blown in, and 15 mL of a dichloromethane solution of intermediate 258-3 (1.0 g) in Example 37 was added dropwise. After the addition was completed, the reaction was allowed to proceed at room temperature for 1 hour. After the reaction was completed, the mixture was purified by column chromatography to obtain 222 mg of compound 301. 1 H NMR (400 MHz, DMSO-d 6) δ 8.15 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 9.6 Hz, 1H), 6.63 (s, 1H), 4.46 (dd, J = 12.3, 2.7 Hz, 1H), 3.97 (dd, J = 12.3, 6.2 Hz, 1H), 3.46 - 3.40 (m, 3H), 3.18 (ddt, J = 6.7, 4.2, 2.6 Hz, 1H), 2.77 (dd, J = 5.0, 4.3 Hz, 1H), 2.62 (dd, J = 5.0, 2.6 Hz, 1H), 1.61 - 1.45 (m, 4H).LCMS (ESI) [M + H] + =507.05, Found =507.10.

[0107] Example 40: Preparation of Compound 302 Step 1: Preparation of Compound 302 [ka] Compound 302 was prepared by following the methods of Examples 38 and 39 and using intermediate 258-3 in Example 37 and (±)-glycidol. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.22 (d, J = 7.8 Hz, 1H), 8.01 (d, J = 9.6 Hz, 1H), 6.69 (s, 1H), 4.52 (dd, J = 12.3, 2.6 Hz, 1H), 4.03 (dd, J = 12.3, 6.3 Hz, 1H), 3.51 - 3.45 (m, 3H), 3.24 (ddt, J = 6.7, 4.2, 2.6 Hz, 1H), 2.83 (dd, J = 5.0, 4.2 Hz, 1H), 2.68 (dd, J = 5.0, 2.6 Hz, 1H), 1.68 - 1.51 (m, 4H).LCMS (ESI) [M + H] + =507.05, Found =506.88.

[0108] Example 41: Measurement of indoor herbicidal activity The herbicidal activity of the compound of the present invention can be tested as follows.

[0109] Before seedlings: A certain amount of seeds of grass family weeds (barnyard grass, goosegrass, Japanese crabgrass, Japanese knotweed, Japanese knotweed, Japanese barnyard grass, Japanese burdock, Japanese grass, Japanese grass, Japanese foxtail, Japanese oak, Japanese bluegrass), broadleaf weeds (Eucalyptus gramineus, Japanese burdock, common mustard, Japanese chickweed, Japanese mugwort, and Japanese hornwort) and Japanese sedge were sown in plastic pots with a diameter of 7 cm and holes at the bottom, filled with nutrient soil (sandy soil, pH 6.1, organic matter 1%). After sowing, the pots were covered with an appropriate amount of soil, the soil was moistened so that water was absorbed from the bottom, and the pots were cultivated in a constant temperature and light incubation room for 24 hours, and sprayed on the soil using a 3WP-2000 type mobile spray tower manufactured by Nanjing Agricultural Mechanization Research Institute, Ministry of Agriculture. Here, the rotation speed of the main shaft was 96 mm / r, the spray height was 300 mm, the effective spray range of the nozzle was 350 mm, and the spray area was 0.35 m 2 The flow rate at the nozzle was 390 mL / min.

[0110] After seedlings: Appropriate amounts of seeds of grass family weeds (barnyard millet, goosegrass, Japanese crabgrass, Japanese knotweed, Japanese knotweed, Japanese barnyard millet, Japanese burdock, Japanese oak, Japanese bluegrass), broadleaf weeds (Eucalyptus gramineus, Japanese burdock, common mustard, Japanese chickweed, Japanese mugwort, and Japanese hornwort) and Japanese sedge were sown in plastic pots with a diameter of 7 cm and holes at the bottom, filled with nutrient soil (sandy soil, pH 6.1, organic matter 1%). After sowing, the pots were covered with an appropriate amount of soil, the soil was moistened so that it would soak up water from the bottom, and the pots were cultivated in a constant temperature and light incubation room until the 2-4 leaf stage, and the stems and leaves were sprayed. After treatment, the solution was left in the shade until it dried naturally in the test room, after which it was cultured in a constant temperature and light incubation room, and the results were evaluated after 21 days.

[0111] Control effect classification criteria: A indicates that the inhibition rate was 85% to 100% or more. B indicates that the inhibition rate was 70% or more and less than 85%. C indicates that the inhibition rate was 55% or more and less than 70%. D indicates that the inhibition rate was less than 55%.

[0112] According to the test results, the compound of formula (I) is 30 g ai / hm 2 At this dosage, excellent control effects were observed against multiple species of weeds, reaching an A-level control effect.

[0113] According to the above test method, some compounds of general formula (I) were selected to carry out parallel herbicidal activity test with compound Butafenacil (compound 47 in the specification) disclosed by US5183492A and compound CK (compound 1 in the specification) disclosed by US5183492A, and the doses used were 7.5 g ai / ha and 15 g ai / ha. The results are shown in Table 2.

[0114] [Table 2] Herbicidal activity of some of the compounds of formula (I) and the control compound (post-seeding, fresh growth inhibition rate %) TIFF0007624525000088.tif106170

[0115] Please note that what has been described above is only the preferred embodiments of the present invention, and those skilled in the art can make many changes and improvements without departing from the concept of the present invention, all of which are within the protection scope of the present invention.

Claims

1. A uracil-based compound containing a carboxylate fragment, the structure of which is represented by the general formula (I): 【Chemistry 1】 In the formula: R 1 and R 2 are each selected from hydrogen or a methyl group, or R 1 and R 2 and form a three-membered ring together with the carbon to which it is attached, R 3 is C 1～3 Alkoxy C 1～3 Alkyl group, C 1～3 Haloalkoxy C 1～3 Alkyl group, C 2～6 Alkenoxy C 1～3 Alkyl group, C 2～6 Haloalkenoxy C 1～3 Alkyl group, C 2～6 Alkynoxy C 1～3 Alkyl group, C 2～6 Haloalkynoxy C 1～3 Alkyl group, C 1～3 AlkylS(O) n C 1～3 Alkyl group, C 3～6 Oxygen-containing cycloalkyl C 1～3 Alkyl group or C 3～9 selected from oxygen-containing cycloalkyl groups; n=0, 1, or 2; R 1 is selected from hydrogen, and R 2 is selected from a methyl group, the carbon atom attached thereto may be selected from the R or S configuration, or is a mixture of the two, wherein in the mixture the ratio of R to S is from 1:99 to 99:

1.

2. 1. A uracil-based compound containing a carboxylate fragment, R 1 and R 2 are each selected from hydrogen or a methyl group, or R 1 and R 2 and form a three-membered ring together with the carbon to which it is attached, R 3 is C 1～3 Alkoxy C 1～3 Alkyl group, C 1～3 Haloalkoxy C 1～3 Alkyl group, C 2～6 Alkenoxy C 1～3 Alkyl group, C 2～6 Haloalkenoxy C 1～3 Alkyl group, C 2～6 Alkynoxy C 1～3 Alkyl group, C 2～6 Haloalkynoxy C 1～3 Alkyl group, C 3～6 Oxygen-containing cycloalkyl C 1～3 Alkyl group or C 3～9 selected from oxygen-containing cycloalkyl groups; R 1 is selected from hydrogen, and R 2 is selected from a methyl group, the carbon atom attached thereto may be selected from the R or S configuration, or is a mixture of the two, in which the ratio of R to S is from 1:99 to 99:

1.

3. 1. A uracil-based compound containing a carboxylate fragment, R 1 and R 2 are each selected from hydrogen or a methyl group; R 3 is C 1～3 Alkoxy C 1～3 Alkyl group, C 1～3 Haloalkoxy C 1～3 Alkyl group, C 2～6 Alkenoxy C 1～3 Alkyl group, C 2～6 Haloalkenoxy C 1～3 Alkyl group, C 2～6 Alkynoxy C 1～3 Alkyl group, C 2～6 Haloalkynoxy C 1～3 Alkyl group, C 3～6 Oxygen-containing cycloalkyl C 1～3 Alkyl group or C 3～9 selected from oxygen-containing cycloalkyl groups; R 1 is selected from hydrogen, and R 2 is selected from a methyl group, the carbon atom attached thereto may be selected from the R or S configuration, or a mixture of the two, in which the ratio of R to S is from 1:99 to 99:

1.

4. A method for preparing a uracil-based compound containing a carboxylic acid ester fragment, comprising contacting an acid compound represented by formula (II) with R3-OH in the presence of a solvent, 【Chemistry 2】 (wherein in general formula (I), (II) and R 3 -OH, the relevant R 1 , R 2 and R 3 The method for producing a uracil compound comprising the carboxylate fragment according to any one of claims 1 to 3, wherein the definitions of are the same as those in claim 1.

5. 5. The method according to claim 4, wherein the reaction temperature is from 0 to 160°C.

6. The method according to claim 4, wherein the reaction time is from 2 to 15 hours.

7. 5. The method according to claim 4, wherein the reaction solvent is at least one selected from dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, toluene, ortho-xylene, meta-xylene, para-xylene, n-heptane, n-octane, and n-nonane.

8. The method according to claim 4, characterized in that the molar ratio of the carboxylic acid compound represented by formula (II) to R 3 -OH used is 1:1 to 4 (wherein the definition of R 3 -OH is the same as that in claim 1).

9. Use of a uracil compound containing the carboxylic acid ester fragment according to any one of claims 1 to 3 for weed control.

10. A composition comprising a uracil compound containing a carboxylic acid ester fragment according to any one of claims 1 to 3 as an active ingredient, the active ingredient content in the composition being 0.1-99.9% by weight.

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