Uracil compound containing aromatic carboxylic acid ester fragment, preparation method therefor, herbicidal composition and use thereof

Abstract

The present invention relates to the field of herbicides, and specifically relates to a uracil compound containing an aromatic carboxylic acid ester fragment as shown in formula (I), a stereoisomer thereof, an agriculturally acceptable salt thereof, a preparation method therefor, a herbicidal composition, and the use thereof in the field of plant protection, wherein R1, R2, R3, R4, Q and X are as defined herein. Compared with the prior art, the uracil compound containing a carboxylic acid ester fragment provided by the present invention has better herbicidal activity and safety.

Description

Uracil compounds containing aromatic carboxylic acid ester fragments, their preparation methods, herbicidal compositions and uses Technical Field

[0001] This invention relates to the field of herbicides, and more specifically to a uracil compound containing an aromatic carboxylic acid ester fragment as shown in formula (I), its stereoisomers, its agriculturally acceptable salts, its preparation method, herbicidal compositions, and their use in the field of plant protection. Background Technology

[0002] Chemical weed control using herbicides is the most economical and effective method for weed control. However, long-term, continuous, and high-dose use of a single herbicide or a herbicide with a single mode of action can easily lead to problems such as herbicide resistance and the evolution of resistance in weeds. Developing new types of pesticides is the core means to solve these problems.

[0003] Protoporphyrinogen oxidase (PPO, EC1.3.3.4) catalyzes the oxidation of protoporphyrinogen IX to protoporphyrin IX, a key enzyme in the same biosynthetic step as chlorophyll and heme. Inhibition of PPO in plants suppresses the synthesis of chlorophyll and heme, causing the substrate protoporphyrinogen IX to exit the normal porphyrin biosynthetic pathway. This results in the rapid export of protoporphyrinogen IX from the chloroplast to the cytoplasm, where it accumulates through non-specific peroxidase and auto-oxidation. The accumulated protoporphyrin IX, in the presence of light and oxygen, produces highly reactive singlet oxygen, which damages the cell membrane and rapidly leads to plant cell death.

[0004] Over the past few decades, PPO has been extensively studied as an important herbicide target. Research on uracil compounds containing aromatic carboxylic acid ester fragments as herbicides has also been frequently reported in patents, such as CN1075716A, WO8810254 A1, CN114621150A, CN117551022A, and DE 4418226A1. Specifically, WO88 / 10254 discloses compounds CK1-CK5, and DE 4418226A1 discloses compounds CK6, CK6-R, and CK6-S.

[0005] However, the weed-control performance and crop selectivity of these known compounds are not entirely satisfactory. Furthermore, due to the expanding market, weed resistance, pesticide lifespan, economic considerations, and increasing environmental awareness, scientists need to continuously research and develop new, highly effective, safe, economical herbicides with different modes of action.

[0006] The prior art does not involve a novel uracil compound containing an aromatic carboxylic acid ester fragment as shown in this invention, its preparation method, herbicidal composition, and application. Summary of the Invention

[0007] This invention provides a uracil compound containing an aromatic carboxylic acid ester fragment as shown in general formula (I), its stereoisomers, and agriculturally acceptable salts thereof:

[0008] In the formula, R1 is selected from C1-C6 haloalkyl groups;

[0009] In the formula, R2 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, cyano, amino, -NR5R6; in the formula, R5 and R6 are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C3-C6 cycloalkyl, respectively.

[0010] In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynylyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl, respectively.

[0011] Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2.

[0012] Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I');

[0013] In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynylyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl; R1, R2, X, and Q in general formula (I') and general formula (Ⅰ) have the same definition;

[0014] X is selected from halogens.

[0015] In general formula (I') and general formula (I), Q represents a three- to eight-membered aromatic heterocycle containing one, two, or three groups selected from O, S, N, NH, CO, SO, or SO2, wherein each atom on the Q group is independently unsubstituted or substituted with a group selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 Or substituted by at least one group in -O-(CO)OR9,

[0016] Alternatively, in general formula (I') and general formula (I), Q represents a three- to eight-membered non-aromatic heterocycle containing one, two, or three groups selected from O, S, N, NH, CO, SO, or SO2, wherein each atom on the Q group is independently unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 Or substituted by at least one group in -O-(CO)OR9;

[0017] In the formula, R9 and R 10 Each is independently selected from hydrogen, C1-C6 alkyl, and C3-C6 cycloalkyl;

[0018] Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine.

[0019] Q is selected from In this case, R3 and R4 are not both hydrogen.

[0020] Preferably,

[0021] In the formula, R1 is selected from C1-C6 haloalkyl groups;

[0022] In the formula, R2 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, cyano, amino, -NR5R6; in the formula, R5 and R6 are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C3-C6 cycloalkyl, respectively.

[0023] In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynylyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl, respectively.

[0024] Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2.

[0025] Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I');

[0026] In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl;

[0027] X is selected from halogens.

[0028] In the formula, Q is unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 The aromatic heterocycles represented by Hy-1 to Hy-7 and Hy-17 to Hy-42, which are substituted by at least one group in -O-(CO)OR9:

[0029] Alternatively, Q in the formula is unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 The non-aromatic heterocyclic groups shown as Hy-8 to Hy-16 and Hy-43 to Hy-126, which are substituted by at least one group in -O-(CO)OR9:

[0030] In the formula, R9 and R 10 Each is independently selected from hydrogen, C1-C6 alkyl, and C3-C6 cycloalkyl;

[0031] In the formula R 11 and R 12 Each is independently selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, and C3-C6 cycloalkyl;

[0032] In the formula, n is selected from 0, 1, or 2;

[0033] Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine.

[0034] Q is selected from In this case, R3 and R4 are not both hydrogen.

[0035] More preferably,

[0036] In the formula, R1 is selected from C1-C4 haloalkyl groups;

[0037] In the formula, R2 is selected from C1-C4 alkyl, amino, and -NR5R6;

[0038] In the formula, R5 and R6 are independently selected from C1-C4 alkyl and C3-C6 cycloalkyl, respectively;

[0039] In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynylyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl, respectively.

[0040] Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2.

[0041] Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I');

[0042] In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6-alkenyl, C2-C6 ynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, and C3-C6 halocycloalkyl;

[0043] X is selected from halogens.

[0044] In the formula, Q is an unsubstituted aromatic heterocyclic group, or a group substituted by at least one of the following groups: halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2, or -O-(CO)OCH3, as shown in Hy-1 to Hy-4, Hy-17 to Hy-20, Hy-22 to Hy-24, and Hy-37.

[0045] Alternatively, Q in the formula is an unsubstituted or non-aromatic heterocyclic group substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2 or -O-(CO)OCH3, as shown in the following groups:

[0046] In the formula R 11 and R 12 Each is independently selected from C1-C4 alkyl groups and C3-C6 cycloalkyl groups;

[0047] In the formula, n is selected from 0, 1, or 2;

[0048] Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine.

[0049] Q is selected from In this case, R3 and R4 are not both hydrogen.

[0050] More preferably,

[0051] In the formula, R1 is selected from C1-C4 haloalkyl groups;

[0052] In the formula, R2 is selected from methyl or amino;

[0053] In the formula, R3 and R4 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, and C3-C6 cycloalkyl-C1-C4 alkyl, respectively.

[0054] Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three-, four-, or five-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2.

[0055] Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I');

[0056] In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, and C3-C6 cycloalkyl-C1-C6 alkyl, respectively;

[0057] X is selected from chlorine or bromine.

[0058] In the formula, Q is an aromatic heterocyclic group shown as Hy-1 to Hy-4, Hy-17 to Hy-20, Hy-22 to Hy-24 and Hy-37, which is either unsubstituted or substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2 or -O-(CO)OCH3.

[0059] Alternatively, Q is an unsubstituted or non-aromatic heterocyclic group represented by Hy-8, Hy-49, Hy-55, Hy-72, and Hy-106 substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2, or -O-(CO)OCH3;

[0060] In the formula R 11 Selected from methyl or cyclopropyl;

[0061] In the formula, n is selected from 0, 1, or 2;

[0062] When R1 is trifluoromethyl, R2 is methyl, X is chlorine, and Q is selected from Hy-49, R3 and R4 are not both hydrogen.

[0063] More preferably,

[0064] In the formula, R1 is selected from -CF3, -CF2H, -CF2CH3 or -CF2Cl;

[0065] In the formula, R2 is selected from methyl or amino;

[0066] In the formula, R3 and R4 are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, or -CH2-(c-C3H5).

[0067] Alternatively, R3 and R4 together with the carbon atoms they are attached to form a fully saturated ternary carbon ring.

[0068] Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I');

[0069] In the formula, R7 and R8 are independently selected from hydrogen, methyl, ethyl or cyclopropyl;

[0070] X is selected from chlorine or bromine.

[0071] In the formula, Q is selected from the aromatic heterocyclic groups shown as Hy-1~Hy-4, Hy-17~Hy-20, Hy-22~Hy-24 and Hy-37;

[0072] Alternatively, Q can be selected from the non-aromatic heterocyclic groups shown as Hy-49, Hy-55, Hy-72, and Hy-106.

[0073] When R1 is trifluoromethyl, R2 is methyl, X is chlorine, and Q is selected from Hy-49, R3 and R4 are not both hydrogen.

[0074] The compounds of formula (I) of the present invention can be described by the specific compounds listed in Table 1, but the present invention is not limited to these compounds.

[0075] Table 1

[0076] The compounds of formula (I') of the present invention can be described by the specific compounds listed in Table 2, but the present invention is not limited to these compounds.

[0077] Table 2

[0078] The method according to the invention for preparing compounds having chemical formula (I) is a method known to those skilled in the art, or a method described in, for example, WO8810254A1, CN114621150A, and WO2021 / 143677A1, comprising the following steps:

[0079] (1) The compound shown in general formula (VII) reacts with the compound shown in general formula (V) or (VI) to produce the compound shown in general formula (IV);

[0080] (2) The compound shown in general formula (IV) undergoes a substitution reaction with a methylating agent to generate methyl uracil arylcarbamate intermediate, which is then subjected to an ester hydrolysis reaction to generate the compound shown in general formula (III).

[0081] (3) The compound shown in general formula (III) reacts with the compound shown in general formula (II) by forming an acyl chloride or by condensation reaction under condensing agent conditions to generate the compound shown in general formula (I).

[0082] In the definitions of compounds of formula (I) given above, the terms used in the compilation are generally defined as follows:

[0083] Alkyl groups refer to saturated straight-chain or branched hydrocarbon groups having a specified number of carbon atoms in each case, such as C1-C6-alkyl groups, including methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, etc. 1-Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl.

[0084] Halogen-substituted alkyl groups (halogenated alkyl groups) refer to the following straight-chain or branched alkyl groups in which some or all of the hydrogen atoms can be replaced by halogen atoms, such as C1-C2 haloalkyl groups, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and 1,1,1-trifluoropropyl-2-yl.

[0085] The term "cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon substituent, wherein the cycloalkyl ring contains 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and most preferably 3 to 6 carbon atoms. Non-limiting examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cyclohepttrienyl, cyclooctyl, etc.; polycyclic cycloalkyl groups include spirocyclic, fused-ring, and bridged-ring cycloalkyl groups, preferably cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, and cycloheptyl.

[0086] The term "halogen" refers to fluorine, chlorine, bromine, or iodine. If the term is used with a group, then "halogen" or "halogen atom" refers to a fluorine, chlorine, bromine, or iodine atom.

[0087] The terms "aromatic heterocycle" or "heteroaryl" have the same meaning, referring to a heteroaryl group containing one or more heteroatoms. Heteratoms referred to herein include oxygen, sulfur, and nitrogen. Examples include furanyl, thiophene, pyridinyl, pyrazolyl, pyrroleyl, N-alkylpyrroleyl, pyrimidinyl, pyrazinyl, imidazolyl, tetrazolyl, etc. The heteroaryl ring may be fused to an aryl, heterocyclic, or cycloalkyl ring, wherein the ring attached to the parent structure is the heteroaryl ring. The heteroaryl group may be optionally substituted or unsubstituted; unless otherwise specified, preferred heteroaryl groups are 5-12 membered heteroaryl groups, more preferably 5-8 membered heteroaryl groups.

[0088] A third aspect of the invention provides the use of aromatic carboxylic acid ester compounds for weed control.

[0089] A fourth aspect of the present invention provides a herbicidal composition comprising an effective amount of at least one of the compounds of general formula I, wherein the compound of general formula I is used as the active component, and the composition contains the active component in a weight percentage of 0.1-99.9%.

[0090] A fifth aspect of the present invention provides a herbicidal composition comprising an effective amount of at least one of the compounds of general formula I, wherein the compound of general formula I is used as the active component, the composition comprising an active component in a weight percentage of 0.1-99.9%, and further comprising a formulation adjuvant.

[0091] A sixth aspect of the invention provides a method for controlling weeds, comprising applying a herbicidal amount of at least one of the compounds of general formula I or the herbicide composition thereof to plants or weedy areas.

[0092] The seventh aspect of the invention provides the use of at least one of the aromatic carboxylic acid ester compounds of general formula I or the herbicide composition thereof in controlling weeds, wherein the aromatic carboxylic acid ester compounds are used to control weeds in useful crops, said useful crops being transgenic crops or crops treated with genome editing technology.

[0093] The compounds of this invention exhibit outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous annual pests, effectively controlling a variety of weeds and achieving good results at low doses, thus making them suitable for use as herbicides. Therefore, this invention also includes the use of compounds of general formula I for weed control.

[0094] Therefore, this invention relates to a method for controlling unwanted plants or for regulating plant growth, wherein one or more compounds of the invention are applied to plants (e.g., harmful plants, such as monocot or dicot weeds or unwanted crop plants), seeds (e.g., grains, seeds, or asexual propagules, such as tubers or budding young shoots), or plant growing areas (e.g., cultivated areas). The compounds of the invention can be applied before planting (and, if appropriate, by introduction into the soil), pre-emergence, or post-emergence. The various representative monocot and dicot weed populations controlled by the compounds of the invention mentioned below are merely illustrative of the invention and are by no means limiting of the invention.

[0095] As mentioned above, the present invention provides a pesticide herbicide composed of an active ingredient and excipients, wherein the active ingredient includes at least one of the aforementioned aromatic carboxylic acid ester compounds.

[0096] In a preferred embodiment, the active ingredient in the pesticide herbicide is present in an amount of 0.1-99.9% by weight.

[0097] The present invention does not impose any particular restrictions on the specific types of excipients in the herbicide, such as various surfactants and solvents commonly used in the field of herbicides.

[0098] The compounds of the present invention can be applied using common formulations, including wettable powders, concentrated emulsions, sprayable solutions, powders, or granules. Thus, the present invention also provides herbicide compositions comprising compounds of formula I. Compounds of formula I can be formulated in various ways depending on typical biological and / or chemical physical parameters. Examples of suitable formulation choices include: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, concentrated emulsions (EC), emulsions such as oil dispersed in water and water dispersed in oil (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions diluted with oil or water, solutions miscible with oil, powders (DP), capsule suspensions (CS), seeddressing compositions, granules for broadcasting and soil application, spray granules, coating granules and absorbent granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low volume) formulations, microcapsules, and wax products.

[0099] The formulation of the active substance may also include thickeners, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, defoamers, evaporation inhibitors, and pH and viscosity adjusters that are commonly used in all cases.

[0100] Based on these formulations, they may also be mixed with other insecticidal active substances such as insecticides, acaricides, herbicides and fungicides, or with safeners, fertilizers and / or plant growth regulators. The mixing method may be pre-mixed or bottled.

[0101] To enhance the control effect of the aromatic carboxylic acid ester compounds of the present invention and expand their application scope, the aromatic carboxylic acid ester compounds of the present invention can be used alone or in combination with other commonly used herbicides. Moreover, there is no particular limitation on the ratio of the combination, which can be selected according to the ratio conventionally used in the art, as long as the control effect after combination can be enhanced, the application scope can be expanded, and the safety can be improved.

[0102] When used, commercially available formulations are diluted in a common manner if necessary, such as with water for wettable powders, concentrated emulsions, suspensions, and granules suspended in water. Powders, granules for soil application, or solutions for broadcasting and spraying generally do not require further dilution with an inert substance before use. The required dosage of Formula I compound varies with external conditions, such as temperature, humidity, and the nature of the herbicide used. It can vary considerably, for example, from 0.001 to 1.0 kg ai / ha, or more active ingredient, but is preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha.

[0103] The compounds of Formula I of the present invention, or salts thereof, are preferably used in the cultivation of economically important genetically modified crops and ornamental plants, such as cereals, including wheat, barley, rye, oats, millet, rice, cassava, and corn, or in the cultivation of sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas, and other vegetable plants. The compounds of Formula I are preferably used as herbicides for the cultivation of useful plants that are resistant or have been genetically engineered to be resistant to the toxic effects of the herbicides.

[0104] Furthermore, the compounds of this invention can significantly regulate crop growth. By modulating plant metabolism, these compounds can be used to directionally control plant components and promote harvesting, for example, by causing plant drying and dwarfing. They are also suitable for regulating and inhibiting unwanted plant growth without disrupting crop growth. Inhibiting plant growth plays a crucial role in many monocot and dicot crops because it can reduce or completely prevent lodging. Detailed Implementation

[0105] The following examples are for illustrative purposes only and should not be construed as limiting the invention in any way. The scope of protection of this invention is defined by the claims. Simple substitutions or modifications made to this invention by those skilled in the art are all within the scope of the technical solutions protected by this invention.

[0106] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be commercially available or prepared by methods known in the literature or as detailed in the description. Those skilled in the art will understand that other synthetic routes can also be used to synthesize the compounds of the present invention. Although specific raw materials and conditions in the synthetic routes have been described below, they can be easily replaced with other similar raw materials and conditions. Such variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are all included within the scope of the present invention. Furthermore, the preparation methods described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, protecting appropriate groups during the reaction process, etc.

[0107] The following method examples are provided to further illustrate the preparation methods of the present invention. The specific substances, types, and conditions used are intended to further explain the invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds described below are either commercially available or can be easily prepared by those skilled in the art.

[0108] The analytical instruments described in the examples are as follows:

[0109] I. High Performance Liquid Chromatography (hereinafter referred to as HPLC): Using an Agilent Technologies 1260 Infinity II instrument.

[0110] Column: Agilent Eclipse Plus C 18 3.5μm, 4.6*100mm

[0111] Mobile phase: A: water + 0.1% phosphoric acid; B: acetonitrile; Temperature: 30℃

[0112] Gradient: 10%B to 95%B over 15 minutes; 95%B over 3 minutes

[0113] Flow rate: 1 mL / min

[0114] II. Ultra-high performance liquid chromatography-tandem mass spectrometry (hereinafter referred to as LC-MS): Using a Waters, ACQUITY H-Class UPLC-SQ Detector 2 instrument.

[0115] column: BEH C 18 1.7μm, 2.1*50mm Column

[0116] Mobile phase: A: Water + 0.2% formic acid; B: Acetonitrile; Temperature: 30℃

[0117] Gradient: 10%B to 95%B over 5 minutes; 95%B over 1 minute

[0118] Flow rate: 0.5 mL / min

[0119] MS method: ESI positive, negative, quality range (m / z): 100-800

[0120] III. Gas Chromatography-Tandem Mass Spectrometry (hereinafter referred to as GC-MS): Using Agilent Technologies, 7890B GC System-5977A MSD equipment.

[0121] Column: Agilent Technologies, HP-5MS UI 0.25μm, 30m*0.250mm

[0122] Injector temperature: 250℃

[0123] Column flow rate: Helium 1 mL / min

[0124] Method: Hold at 40℃ for 2 min, increase temperature to 280℃ at 20℃ / min, hold at 280℃ for 5 min, total time 19 min.

[0125] MSD transmission line temperature: 280℃

[0126] EI ion source temperature: 230℃, MS quadrupole temperature: 150℃, scan range: 30.00-400.00

[0127] In addition, the proton nuclear magnetic resonance spectra described below (hereinafter referred to as...) 1 The chemical shift values ​​of H-NMR were measured at 400 MHz (Bruker, AVANCE III HD 400M) in deuterated chloroform (CDCl3) using Me4Si (tetramethylsilane) as the reference material. When measured in deuterated dimethyl sulfoxide, the chemical shift values ​​are shown as "(DMSO-d6)" in the data. It should be noted that... 1 The symbols in the chemical shift values ​​of H-NMR represent the following meanings:

[0128] s: singlet, d: doublet, dd: doublett, dt: doublettuplet, td: triplettuplet, ddd: doublettuplet, t: triplet, q: quartet, sep: septet, m: multiplet, brs: broad singlet. Furthermore, in cases where two or more stereoisomers are present, the chemical shift values ​​for the resolvable signal are marked with "and".

[0129] Examples of representative compounds are given below. The synthesis methods of other compounds are similar and will not be described in detail here.

[0130] Example 1: Preparation of compounds 1-8

[0131] At room temperature, 2-pyridin-2-propanol (71 mg, 0.52 mmol), 4-dimethylaminopyridine (256 mg, 2.1 mmol), and dichloromethane (10 mL) were added to a 25 mL single-necked flask. A solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (200 mg, 0.52 mmol) (synthetic method according to the preparation of intermediates 1-8 in patent CN 114621150 A) in dichloromethane (0.5 mL) was slowly added dropwise, and the reaction was allowed to proceed for 1 h. After the reaction was complete, compounds 1-8 (white solid, 45 mg) were purified by silica gel column chromatography.

[0132] MRI: 1 H NMR (400MHz, DMSO-d6) δ8.53(d,J=4.7Hz,1H),8.09(d,J=7.8Hz,1H),7.88(d,J=9.6Hz,1H),7.81(td,J=7 .7,1.6Hz,1H),7.51(d,J=8.0Hz,1H),7.30(dd,J=7.4,4.9Hz,1H),6.63(s,1H),3.43(s,3H),1.83(s,6H).

[0133] Example 2: Preparation of compounds 2-8

[0134] At room temperature, 2-(pyrimidin-2-yl)prop-2-ol (107 mg, 0.78 mmol), 4-dimethylaminopyridine (190 mg, 1.56 mmol), triethylamine (218 μL, 1.56 mmol), and dichloromethane (10 mL) were added to a 25 mL single-necked flask. A solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (300 mg, 0.78 mmol) in dichloromethane (1 mL) was slowly added dropwise, and the reaction was allowed to proceed for 1 h. After the reaction was complete, the solution was purified by silica gel column chromatography to obtain compound 2-8 (white solid, 68 mg).

[0135] MRI: 1H NMR (400MHz, DMSO-d6) δ9.15(s,1H),8.95(s,2H),8.10(d,J=7.8Hz,1H),7.89(d,J=9.6Hz,1H),6.64(s,1H),3.43(s,3H),1.91(s,6H).

[0136] Example 3: Preparation of compounds 4-8

[0137] At room temperature, 2-(pyrimidin-4-yl)prop-2-ol (107 mg, 0.78 mmol), 4-dimethylaminopyridine (190 mg, 1.56 mmol), triethylamine (218 μL, 1.56 mmol), and dichloromethane (10 mL) were added to a 25 mL single-necked flask. A solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (300 mg, 0.78 mmol) in dichloromethane (1 mL) was slowly added dropwise, and the reaction was allowed to proceed for 1 h. After the reaction was complete, the reaction solution was directly purified by silica gel column chromatography to give compound 4-8 (white solid, 22 mg).

[0138] MRI: 1 H NMR (400MHz, DMSO-d6) δ9.16 (s, 1H), 8.82 (d, J = 5.4Hz, 1H), 8.13 (d, J = 7.8Hz, 1H), 7.9 0(d,J=9.6Hz,1H),7.64(dd,J=5.3,0.9Hz,1H),6.63(s,1H),3.43(s,3H),1.82(s,6H).

[0139] Example 4: Preparation of compound 5-2

[0140] At room temperature, 1-(oxazol-2-yl)acetic-1-ol (60 mg, 0.53 mmol), 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (300 mg, 0.78 mmol), dichloromethane (5 mL), and 4-dimethylaminopyridine (286 mg, 2.34 mmol) were added to a 48 mL pressure-resistant flask and stirred overnight at 40 °C. After the reaction was complete, 10 mL of water was added to the reaction system, and the mixture was extracted twice with 15 mL of ethyl acetate. The combined organic phases were washed once with saturated brine. The mixture was dried over anhydrous sodium sulfate, the solvent was removed by vacuum distillation, and the concentrated organic phase was purified by silica gel column chromatography to give compound 5-2 (white solid, 230 mg).

[0141] MRI:1 H NMR (400MHz, CDCl3) δ7.92(d,J=7.7Hz,1H),7.66(d,J=0.8Hz,1H),7.39(d,J=9.2Hz,1H),7.12(s,1H), 6.37(d,J=2.0Hz,1H), 6.23(qd,J=6.7,1.2Hz,1H), 3.56(dt,J=2.6,1.3Hz,3H), 1.79(d,J=6.7Hz,3H).

[0142] Example 5: Preparation of compound 12-2

[0143] At room temperature, compound 1-(1-methyl-1H-1,2,4-triazol-3-yl)ethanol-1-ol (120 mg, 0.94 mmol), 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (500 mg, 1.31 mmol), dichloromethane (5 mL), and 4-dimethylaminopyridine (344 mg, 2.82 mmol) were added to a 48 mL pressure-resistant flask and stirred overnight at 40 °C. After the reaction was complete, 10 mL of water was added to the reaction system, and the mixture was extracted twice with 15 mL of ethyl acetate. The combined organic phases were washed once with saturated brine. The mixture was dried over anhydrous sodium sulfate, and the concentrated organic phase was purified by silica gel column chromatography to give compound 12-2 (white solid, 90 mg).

[0144] MRI 1 H NMR (400MHz, CDCl3) δ8.00(s,1H),7.94(d,J=7.7Hz,1H),7.37(d,J=9.2Hz,1H),6.36(d,J =5.6Hz,1H),6.29–6.20(m,1H),3.89(s,3H),3.55(d,J=5.4Hz,3H),1.75(d,J=6.7Hz,3H).

[0145] Example 6: Preparation of compounds 13-8

[0146] Step 1: Preparation of intermediate 2-(tetrahydrofuran-2-yl)prop-2-ol

[0147] At room temperature, methyl tetrahydrofuran-2-carboxylate (1.0 g, 7.68 mmol) and anhydrous tetrahydrofuran (20 mL) were added to a 100 mL single-necked flask. A 3M tetrahydrofuran solution of magnesium methyl chloride (6.4 mL, 19.2 mmol) was slowly added dropwise under ice bath conditions, followed by stirring at room temperature for 2 h. After the reaction was complete, the reaction solution was quenched with saturated ammonium chloride solution (20 mL), the tetrahydrofuran layer was separated, and the aqueous phase was extracted five times with ethyl acetate (50 mL × 5). The organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain compound 2-(tetrahydrofuran-2-yl)prop-2-ol (yellow oil, 0.54 g), which was used directly in the next step.

[0148] MRI: 1 H NMR(400MHz, DMSO-d6)δ4.11(s,1H),3.73(dd,J=10.1,4.2Hz,1H),3.62(dd,J=12.4, 6.3Hz,1H),3.53(dd,J=9.3,4.7Hz,1H),1.81–1.68(m,4H),1.05(s,3H),1.03(s,3H).

[0149] Step 2: Preparation of Compounds 13-8

[0150] At room temperature, 2-(tetrahydrofuran-2-yl)prop-2-ol (200 mg, 1.54 mmol), 4-dimethylaminopyridine (316 mg, 2.59 mmol), and dichloromethane (10 mL) were added to a 50 mL single-necked flask. A solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (500 mg, 1.29 mmol) in dichloromethane (5 mL) was slowly added dropwise, and the reaction was allowed to proceed for 2 h. After the reaction was complete, the solution was purified by silica gel column chromatography to obtain compound 13-8 (white solid, 112 mg).

[0151] MRI: 1 H NMR (400MHz, DMSO-d6): δ7.89(d,J=7.8Hz,1H),7.84(d,J=9.6Hz,1H),6.61(s,1H),4.06(t, J=6.7Hz,1H),3.81–3.66(m,2H),3.42(s,3H),1.96–1.75(m,4H),1.54(s,3H),1.53(s,3H).

[0152] Example 7: Preparation of compounds 13-10

[0153] At room temperature, compound 1-(tetrahydrofuran-2-yl)cycloprop-1-ol (60.0 mg, 0.52 mmol) (synthetic method according to Organic Letters 21.8 (2019): 2615-2619.), 4-dimethylaminopyridine (10.0 mg, 0.036 mmol), triethylamine (110 μL, 0.78 mmol), and dichloromethane (5 mL) were added to a 25 mL single-necked flask. A solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (200 mg, 0.52 mmol) in dichloromethane (0.5 mL) was slowly added dropwise, and the reaction was allowed to proceed for 1 h. After the reaction was complete, compound 13-10 (white solid, 127 mg) was purified by silica gel column chromatography.

[0154] MRI: 1 H NMR(400MHz, CDCl3)δ7.85(d,J=7.7Hz,1H),7.37(d,J=9.2Hz,1H),6.37(s,1H),4.44–4.29(m,1H),3.87 –3.70(m,2H),3.57(s,3H),2.07–1.97(m,1H),1.99–1.84(m,2H),1.78–1.63(m,1H),1.16–0.87(m,4H).

[0155] Example 8: Preparation of compound 15-2

[0156] Step 1: Preparation of intermediate 1,1-dimethoxyprop-2-ol

[0157] At room temperature, acetone dimethyl acetal (5.0 g, 42 mmol) and methanol (50 mL) were added to a 250 mL single-necked flask. Sodium borohydride (1.6 g, 42 mmol) was slowly added under ice bath conditions, and the mixture was stirred at room temperature for 2 h. After the reaction was complete, water (5 mL) was added to the reaction solution to quench the reaction, and the solvent was removed by vacuum distillation. The solution was purified by silica gel column chromatography to obtain 1,1-dimethoxyprop-2-ol (colorless liquid, 2.7 g).

[0158] Step 2: Preparation of intermediate 1,1-dimethoxypropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate

[0159] At room temperature, 1,1-dimethoxyprop-2-ol (2.7 g, 23.4 mmol), triethylamine (3.96 mL, 28.08 mmol), 4-dimethylaminopyridine (36 mg, 2.7 mmol), and 20 mL of dichloromethane were added to a 100 mL single-necked flask. Then, 10 mL of a dichloromethane solution of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (9.0 g, 23.4 mmol) was added dropwise, and the mixture was allowed to react at room temperature for 1 h. After the reaction was completed, the concentrated reaction solution was purified by silica gel column chromatography to obtain 1,1-dimethoxypropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (white solid, 5.2 g).

[0160] Step 3: Preparation of 1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate

[0161] At room temperature, 1,1-dimethoxypropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (5.2 g, 11.1 mmol), 2M hydrochloric acid solution (10 mL), and tetrahydrofuran (50 mL) were added to a 250 mL single-necked flask, and the mixture was heated to 60 °C and reacted for 8 h. After the reaction was completed, water (50 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (50 mL × 3). The organic phases were combined, washed successively with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated to obtain 1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (colorless oil, 4.5 g).

[0162] Step 4: Preparation of Compound 15-2

[0163] At room temperature, 1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (500 mg, 1.18 mmol), ethylene glycol (147 mg, 2.37 mmol), p-toluenesulfonic acid (20 mg, 0.12 mmol), and toluene (5 mL) were added to a 25 mL single-necked flask, and the mixture was heated to reflux and reacted for 30 minutes. After the reaction was completed, the concentrated reaction solution was purified by silica gel column chromatography to give compound 15-3 (white solid, 154 mg).

[0164] MRI: 1 H NMR(400MHz, DMSO-d6)δ8.02(d,J=7.6Hz,1H),7.91(d,J=9.6Hz,1H),6.63(s,1H),5.14–5.04(m,1H ),4.98(d,J=4.1Hz,1H),3.96–3.90(m,2H),3.88–3.80(m,2H),3.42(s,3H),1.29(d,J=6.5Hz,3H).

[0165] Example 9: Preparation of Compounds 15-8

[0166] Step 1: Synthesis of intermediate 2-bromo-2-methylpropanal

[0167] At room temperature, 5.0 g (70 mmol) of 2-bromo-2-methylpropanal and 50 mL of dichloromethane were added to a 250 mL single-necked flask. The mixture was cooled to 0 °C, and 20 mL of a dichloromethane solution containing 3.5 mL (70 mmol) of bromine was slowly added dropwise with stirring. The reaction mixture was then heated to room temperature and reacted for 30 minutes. After the reaction was complete, 50 mL of water was added to the reaction mixture. The organic phase was separated and washed with saturated sodium bicarbonate solution. The aqueous phase was extracted with dichloromethane (30 mL). The organic phases were combined and washed with saturated sodium chloride solution. The mixture was dried over anhydrous sodium sulfate and the organic phase was concentrated to obtain 6.7 g (brown oily substance), which was used directly in the next step.

[0168] Step 2: Preparation of intermediate 2-methyl-1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate

[0169] At room temperature, 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid (1.0 g, 2.7 mmol) (synthetic method refers to the preparation of intermediates 1-7 in patent CN 114621150 A), anhydrous potassium carbonate (0.56 mg, 4.1 mmol), and N,N-dimethylformamide (10 mL) were added to a 50 mL single-necked flask, and 2-bromo-2-methylpropanal (85 mg, 0.56 mmol) was added dropwise. The mixture was stirred at room temperature for 2 h. After the reaction was complete, water (20 mL) was added to the reaction solution, and the mixture was extracted with ethyl acetate (20 mL × 3). The organic phases were combined, washed successively with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the organic phase was concentrated to obtain 2-methyl-1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (yellow oil, 0.8 g), which was used directly in the next step.

[0170] Step 3: Preparation of Compounds 15-8

[0171] At room temperature, 2-methyl-1-oxopropyl-2-yl-2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoate (150 mg, 0.34 mmol), ethylene glycol (42 mg, 0.68 mmol), p-toluenesulfonic acid (6 mg, 0.034 mmol), and toluene (5 mL) were added to a 25 mL single-necked flask, and the mixture was heated to reflux and reacted for 0.5 h. After the reaction was completed, the concentrated reaction solution was purified by silica gel column chromatography to give compound 15-8 (white solid, 131 mg).

[0172] MRI: 1 H NMR(400MHz,DMSO-d6)δ7.91(d,J=7.8Hz,1H),7.87(d,J=9.6Hz,1H),6.61(s,1H ),5.06(s,1H),3.98–3.91(m,2H),3.91–3.83(m,2H),3.42(s,3H),1.53(s,6H).

[0173] Example 10: Preparation of compounds CK1-CK5

[0174] Compounds CK1-CK5 were synthesized using the method described in patent WO88 / 10254, with 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid and epichlorohydrin as raw materials. Compound CK1 was synthesized using 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride as raw material, and reacted with 3-methyl-3-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, glycerol formaldehyde, and acetone glycerol, respectively, to synthesize compounds CK2-CK5.

[0175] Example 11: Preparation of compounds CK6, CK6-R and CK6-S

[0176] Step 1: Preparation of compound 2-chloro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride

[0177] 2-Chloro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid (2.0 g, 5.74 mmol) (synthetic method according to the synthesis of intermediate O in patent WO2018122559 A1) and N,N-dimethylformamide (20.0 mg, 0.29 mmol) were added to dichloromethane (20 mL), and oxalyl chloride (1.09 g, 8.60 mmol) was added dropwise to the reaction solution. The reaction was carried out at room temperature for 1 h. After the reaction was completed, the concentrated reaction solution was used directly for the next step.

[0178] Step 2: Preparation of compounds CK6, CK6-R and CK6-S

[0179] 2-(1-hydroxyethyl)pyridine (167.7 mg, 1.36 mmol) and triethylamine (206.74 mg, 2.04 mmol) were added to dichloromethane (10 mL). A solution of 2-chloro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride (500.0 mg, 1.36 mmol) in dichloromethane (2 mL) was slowly added dropwise to the reaction mixture, and the reaction was allowed to proceed for 1 h. After the reaction was complete, the compound CK6 (white solid, 188 mg) was purified by silica gel column chromatography.

[0180] Compounds CK6-R and CK6-S were synthesized using a similar method described above. They were prepared by reacting (R)-2-(1-hydroxyethyl)pyridine and (S)-2-(1-hydroxyethyl)pyridine, respectively, with 2-chloro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride.

[0181] Compounds 1-1 to 16-60 were prepared in a manner similar to the preparation examples given above.

[0182] The analytical data of compounds 1-1 to 16-60 and CK1-CK5, CK6, CK6-S and CK6-R in the examples are shown in Table 3 below.

[0183] Table 3 shows the analytical data for compound formula (I).

[0184] Example 12: Indoor herbicidal activity test

[0185] The herbicidal activity test method for the compounds of this invention is as follows:

[0186] Pre-emergence: Quantities of gramineous weeds (barnyard grass, goosegrass, crabgrass, Japanese alfalfa, wild oats, barnyard grass, wild oats, flowering ryegrass, Kentucky bluegrass), broadleaf weeds (eclipta prostrata, amaranth, wild rapeseed, chickweed, fleabane, sesbania) and rice rice grass seeds were sown separately in 7cm diameter plastic pots with holes at the bottom, filled with nutrient soil (sandy soil, pH 6.1, 1% organic matter). After sowing, a suitable amount of soil was covered, and the soil was moistened by bottom watering. The pots were then placed in a constant temperature and light incubator for 24 hours before soil spraying. Spraying was performed using a 3WP-2000 mobile spray tower manufactured by the Nanjing Agricultural Mechanization Research Institute of the Ministry of Agriculture, with a main shaft speed of 96mm / r, a spray height of 300mm, an effective nozzle width of 350mm, and a spray area of ​​0.35m². 2 The nozzle flow rate is 390 mL / min.

[0187] Post-emergence: Appropriate amounts of seeds of gramineous weeds (barnyard grass, goosegrass, crabgrass, Japanese alfalfa, wild oats, barnyard grass, wild oats, flowering ryegrass, Kentucky bluegrass), broadleaf weeds (eclipta prostrata, amaranth, wild rapeseed, chickweed, fleabane, sesbania), and sedges were sown separately in 7cm diameter plastic pots filled with nutrient soil (sandy soil, pH 6.1, 1% organic matter) with holes at the bottom. After sowing, a suitable amount of soil was covered, and the soil was moistened by bottom watering. The pots were then placed in a constant temperature and light incubator until the 2-4 leaf stage, at which point foliar spraying was applied. After treatment, the materials were placed in the laboratory to allow the pesticide solution to air dry naturally before being placed in a constant temperature and light incubator for 21 days. Results were measured after this period.

[0188] Grading standards for prevention and control effectiveness:

[0189] A indicates that the fresh weight inhibition rate is greater than or equal to 80% to 100%;

[0190] B indicates that the fresh weight inhibition rate is greater than or equal to 60% and less than 80%;

[0191] C indicates that the fresh weight inhibition rate is greater than or equal to 40% and less than 60%;

[0192] D indicates that the fresh weight inhibition rate is greater than or equal to 20% and less than 40%;

[0193] E indicates that the fresh weight inhibition rate is less than 20%.

[0194] Experimental results show that compound of general formula I at 30 g ai / hm 2 It exhibits excellent control effects against a wide variety of weeds at the appropriate dosage.

[0195] Table 4: Some compounds of general formula I at 30 g ai / hm 2 Herbicidal activity at dosage (post-emergence, fresh weight inhibition rate %) NT = Not test

[0196] Table 5: Some compounds of general formula I at 30 g ai / hm 2 Herbicidal activity at dosage (pre-emergence, fresh weight inhibition rate %) NT = Not test

[0197] Following the above testing method, parallel tests were conducted on the herbicidal activity of selected compounds of general formula (I) and compounds CK1-CK5 specifically disclosed in patent WO 88 / 10254, with an application dose of 10 g ai / ha. The results are shown in Table 6:

[0198] Table 6: Herbicidal activity of some compounds of general formula I and control compounds (post-emergence, fresh weight inhibition rate %)

[0199] Following the above testing method, parallel tests were conducted on the herbicidal activity of selected compounds of general formula (I) and the compounds CK6, CK6-R, and CK6-S specifically disclosed in DE 4418226A1, with an application rate of 10 g ai / ha. The results are shown in Table 7.

[0200] Table 7: Herbicidal activity of some compounds of general formula I and control compounds (post-emergence, fresh weight inhibition rate %)

[0201] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several changes and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A uracil compound containing an aromatic carboxylic acid ester fragment as shown in general formula (I), its stereoisomers, and agriculturally acceptable salts thereof: In the formula, R1 is selected from C1-C6 haloalkyl groups; In the formula, R2 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, cyano, amino, -NR5R6; in the formula, R5 and R6 are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C3-C6 cycloalkyl, respectively. In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl, respectively. Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2. Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I'); In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl; X is selected from halogens; In the formula, Q represents a three- to eight-membered aromatic heterocycle containing one, two, or three groups selected from O, S, N, NH, CO, SO, or SO2. Each atom in the Q group is independently unsubstituted or substituted with a group selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R. 10 Or substituted by at least one group in -O-(CO)OR9, Alternatively, Q represents a three- to eight-membered non-aromatic heterocycle containing one, two, or three groups selected from O, S, N, NH, CO, SO, or SO2, wherein each atom on the Q group is independently unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 Or substituted by at least one group in -O-(CO)OR9; In the formula, R9 and R 10 Each is independently selected from hydrogen, C1-C6 alkyl, and C3-C6 cycloalkyl; Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine. Q is selected from In this case, R3 and R4 are not both hydrogen.

2. The compound of formula (I) according to claim 1, its stereoisomers, and agriculturally acceptable salts thereof: In the formula, R1 is selected from C1-C6 haloalkyl groups; In the formula, R2 is selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, cyano, amino, -NR5R6; in the formula, R5 and R6 are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, and C3-C6 cycloalkyl, respectively. In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl, respectively. Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2. Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I'); In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl; X is selected from halogens; In the formula, Q is unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 The aromatic heterocycles represented by Hy-1 to Hy-7 and Hy-17 to Hy-42, which are substituted by at least one group in -O-(CO)OR9: Alternatively, Q in the formula is unsubstituted or selected from halogen, cyano, amino, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 ynyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloynyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl substituted with C1-C4 alkyl or halogen, -OR9, -SR9, -SOR9, -(SO2)R9, -(CO)OR9, -NR9R 10 The non-aromatic heterocyclic groups shown as Hy-8 to Hy-16 and Hy-43 to Hy-126, which are substituted by at least one group in -O-(CO)OR9: In the formula, R9 and R 10 Each is independently selected from hydrogen, C1-C6 alkyl, and C3-C6 cycloalkyl; In the formula R 11 and R 12 Each is independently selected from C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, and C3-C6 cycloalkyl; In the formula, n is selected from 0, 1, or 2; Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine. Q is selected from In this case, R3 and R4 are not both hydrogen.

3. The compound of formula (I) according to claim 2, its stereoisomers, and its agriculturally acceptable salts: In the formula, R1 is selected from C1-C4 haloalkyl groups; In the formula, R2 is selected from C1-C4 alkyl, amino, and -NR5R6; In the formula, R5 and R6 are independently selected from C1-C4 alkyl and C3-C6 cycloalkyl, respectively; In the formula, R3 and R4 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl, respectively. Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three- to eight-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2. Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I'); In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl-C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, and C3-C6 halocycloalkyl; X is selected from halogens; In the formula, Q is an unsubstituted aromatic heterocyclic group, or a group substituted by at least one of the following groups: halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2, or -O-(CO)OCH3, as shown in Hy-1 to Hy-4, Hy-17 to Hy-20, Hy-22 to Hy-24, and Hy-37. Alternatively, Q in the formula is an unsubstituted or non-aromatic heterocyclic group substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2 or -O-(CO)OCH3, as shown in the following groups: In the formula R 11 and R 12 Each is independently selected from C1-C4 alkyl groups and C3-C6 cycloalkyl groups; In the formula, n is selected from 0, 1, or 2; Where R1 is trifluoromethyl, R2 is methyl, and X is chlorine. Q is selected from In this case, R3 and R4 are not both hydrogen.

4. The compound of formula (I) according to claim 3, its stereoisomers, and its agriculturally acceptable salts: In the formula, R1 is selected from C1-C4 haloalkyl groups; In the formula, R2 is selected from methyl or amino; In the formula, R3 and R4 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, and C3-C6 cycloalkyl-C1-C4 alkyl, respectively. Alternatively, R3 and R4 together with the carbon atoms they are attached to form saturated or unsaturated three-, four-, or five-membered carbon rings, or saturated or unsaturated heterocycles containing one, two, or three heteroatoms selected from O, S, N, NH, CO, or SO2. Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I'); In the formula, R7 and R8 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, and C3-C6 cycloalkyl-C1-C6 alkyl, respectively; X is selected from chlorine or bromine; In the formula, Q is an aromatic heterocyclic group shown as Hy-1 to Hy-4, Hy-17 to Hy-20, Hy-22 to Hy-24 and Hy-37, which is either unsubstituted or substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2 or -O-(CO)OCH3. Alternatively, Q is an unsubstituted or non-aromatic heterocyclic group represented by Hy-8, Hy-49, Hy-55, Hy-72, and Hy-106 substituted by at least one group selected from halogen, cyano, amino, nitro, methyl, cyclopropyl, trifluoromethyl, halocyclopropyl, -OCH3, -SCH3, -SOCH3, -(SO2)CH3, -(CO)OCH3, -N(CH3)2, or -O-(CO)OCH3; In the formula R 11 Selected from methyl or cyclopropyl; In the formula, n is selected from 0, 1, or 2; When R1 is trifluoromethyl, R2 is methyl, X is chlorine, and Q is selected from Hy-49, R3 and R4 are not both hydrogen.

5. The compound of formula (I) according to claim 4, its stereoisomers, and its agriculturally acceptable salts: In the formula, R1 is selected from -CF3, -CF2H, -CF2CH3 or -CF2Cl; In the formula, R2 is selected from methyl or amino; In the formula, R3 and R4 are independently selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, or -CH2-(c-C3H5). Alternatively, R3 and R4 together with the carbon atoms they are attached to form a fully saturated ternary carbon ring. Alternatively, R3 and R4 together with the carbon atoms they are attached to form double bonds, which are optionally replaced by R7 and R8 according to the following formula (I'); In the formula, R7 and R8 are independently selected from hydrogen, methyl, ethyl or cyclopropyl; X is selected from chlorine or bromine; In the formula, Q is selected from the aromatic heterocyclic groups shown as Hy-1~Hy-4, Hy-17~Hy-20, Hy-22~Hy-24 and Hy-37; Alternatively, Q can be selected from the non-aromatic heterocyclic groups shown as Hy-49, Hy-55, Hy-72, and Hy-106. When R1 is trifluoromethyl, R2 is methyl, X is chlorine, and Q is selected from Hy-49, R3 and R4 are not both hydrogen.

6. A method for preparing the uracil compound (I) containing an aromatic carboxylic acid ester fragment as described in any one of claims 1 to 5, its stereoisomers, and agriculturally acceptable salts thereof, the method comprising the following steps: (1) The compound shown in general formula (III) and the compound shown in general formula (II) react by forming an acyl chloride or by condensation under condensing agent conditions to produce the compound shown in general formula (I).

7. The use of the uracil compound (I) containing an aromatic carboxylic acid ester fragment as described in any one of claims 1 to 5, its stereoisomers, and its agriculturally acceptable salts for weed control.

8. A herbicidal composition, characterized in that, It includes at least one of the uracil compound (I) containing an aromatic carboxylic acid ester fragment as described in any one of claims 1 to 5, its stereoisomers and agriculturally acceptable salts, wherein the active component is a compound of general formula I, and the composition contains the active component in a weight percentage of 0.1-99.9%.

9. A herbicidal composition, characterized in that, It includes at least one of the uracil compound (I) containing an aromatic carboxylic acid ester fragment as described in any one of claims 1 to 5, its stereoisomers and agriculturally acceptable salts, wherein the active component is a compound of general formula I, and the composition contains an active component in a weight percentage of 0.1-99.9%, and also includes a formulation adjuvant.

10. A method for controlling weeds, characterized in that, It includes using at least one of the herbicidal effective amounts of the uracil compound (I) containing an aromatic carboxylic acid ester fragment as described in any one of claims 1 to 5, its stereoisomers, and its agriculturally acceptable salts on plants or in weedy areas.

11. A method for controlling weeds, characterized in that, It includes applying an effective amount of the herbicide composition of claim 8 to plants or weedy areas.

12. A method for controlling weeds, characterized in that, It includes applying an effective amount of the herbicide composition of claim 9 to plants or weedy areas.

13. Use of at least one of the aromatic carboxylic acid ester fragment-containing uracil compound (I), its stereoisomer, and its agriculturally acceptable salt as described in any one of claims 1 to 5 for weed control, wherein the aromatic carboxylic acid ester-containing compound is used to control weeds in a useful crop, said useful crop being a transgenic crop or a crop treated with genome editing technology.

14. Use of the herbicidal composition of claim 8 in controlling weeds, wherein the uracil compound (I) containing an aromatic carboxylic acid ester fragment, its stereoisomers, and its agriculturally acceptable salts are used to control weeds in a useful crop, said useful crop being a transgenic crop or a crop treated with genome editing technology.

15. Use of the herbicidal composition of claim 9 in controlling weeds, wherein the uracil compound (I) containing an aromatic carboxylic acid ester fragment, its stereoisomers, and its agriculturally acceptable salts are used to control weeds in a useful crop, said useful crop being a transgenic crop or a crop treated with genome editing technology.

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