A phenoxypropionic propyl ester compound, a preparation method thereof and application thereof as a herbicide

Abstract

A phenoxypropionic propyl ester compound, a preparation method thereof, a composition containing the same, and an application of the same as a herbicide. The structure of the phenoxypropionic propyl ester compound is shown in formula (I), wherein the definitions of each substituent are described in detail in the specification.

Description

Technical Field

[0001] This article relates to, but is not limited to, agricultural chemical technology, particularly a propyl phenoxypropionate compound, its preparation method, and its application as an active ingredient in herbicides. Background Technology

[0002] Due to long-term use of herbicides, weed resistance has emerged. Reduced efficacy and significant environmental pollution are major factors limiting the effectiveness of herbicides, making the development of new herbicides an urgent priority. Summary of the Invention

[0003] This application provides a novel propyl phenoxypropionate compound that has herbicidal activity.

[0004] In a first aspect, this application provides a propyl phenoxypropionate compound, said propyl phenoxypropionate compound, as shown in formula (I), or a stereoisomer, solvate, hydrate, or a chemically acceptable salt thereof:

[0005]

[0006] In equation (I), R1 is an optional substituted C3-C 10 Azaaryl;

[0007] R2, R3, R4, R5 and R6 are each independently selected from hydrogen, halogen, unsubstituted C1-C4 alkyl or C1-C4 haloalkyl.

[0008] In some embodiments, compound (I) is compound (II):

[0009]

[0010] The definitions of each substituent in equation (II) are the same as those in equation (I).

[0011] In some embodiments, the addition acid in formula (I) or formula (II) is an inorganic acid or an organic acid; the inorganic acid may be selected from hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid; the organic acid may be selected from...

[0012] In some implementations, R1 in formula (I) or formula (II) is unsubstituted C3-C 10 Azaaryl.

[0013] In some implementations, R1 in formula (I) or formula (II) is a substituted C3-C 10 Azaaryl, wherein the substituted C3-C 10 Azaaryl refers to a group that is substituted by one or more of the following groups: halogens, unsubstituted C1-C4 alkyl groups, and C1-C4 haloalkyl groups.

[0014] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl groups: fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, halomethyl, haloethyl, halon-n-propyl, haloisopropyl, halon-n-butyl, haloisobutyl, and halotert-butyl.

[0015] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl groups: fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and trifluoromethyl.

[0016] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl groups: fluorine, chlorine, and trifluoromethyl.

[0017] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl: Fluorine.

[0018] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl: chlorine and trifluoromethyl.

[0019] In some embodiments, R1 in formula (I) or formula (II) is a C3-C group substituted with one or more of the following groups. 10 Azaaryl: Trifluoromethyl.

[0020] In some implementations, the C3-C 10 The azirroyl group is selected from one of the following groups: pyridyl, quinoxaloyl (i.e., 1,4-diazanaphthyl) or benzoxazolyl.

[0021] In some implementations, the C3-C 10 The azirroyl group is selected from one of the following groups: pyridin-2-yl, quinoxalin-2-yl, or benzoxazol-2-yl.

[0022] In some embodiments, R1 in formula (I) or formula (II) is one or more of the following groups substituted by fluorine, chlorine and trifluoromethyl: pyridinyl, quinoxaloline (i.e. 1,4-diazonyl) and benzoxazolyl.

[0023] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl.

[0024] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl.

[0025] In some embodiments, R1 in formula (I) or formula (II) is 3,5-dichloropyridin-2-yl.

[0026] In some embodiments, R1 in formula (I) or formula (II) is 3-fluoro-5-chloro-pyridin-2-yl.

[0027] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl.

[0028] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazole-2-yl.

[0029] In some embodiments, R2, R3, R4, R5 and R6 in formula (I) or formula (II) are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, halomethyl, haloethyl, halon-n-propyl, haloisopropyl, halon-n-butyl, haloisobutyl and halotert-butyl.

[0030] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is hydrogen.

[0031] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is fluorine, chlorine, bromine or iodine.

[0032] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is fluorine.

[0033] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is chlorine.

[0034] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is a halomethyl, haloethyl, halopropyl, haloisopropyl, halobutyl, haloisobutyl or halotert-butyl.

[0035] In some embodiments, at least one of the groups R2, R3, R4, R5 and R6 in formula (I) or formula (II) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

[0036] In some embodiments, R2 and R3 in formula (I) or formula (II) are both hydrogen; at least one of R4, R5 and R6 is fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

[0037] In some embodiments, R2 and R3 in formula (I) or formula (II) are both hydrogen; at least one of R4, R5 and R6 is fluorine or chlorine.

[0038] In some embodiments, R2 and R3 in formula (I) or formula (II) are both hydrogen; at least one of R4 and R5 is fluorine or chlorine, while the other is hydrogen; and R6 is hydrogen, chlorine, fluorine, or methyl.

[0039] In some embodiments, R2 and R3 in formula (I) or formula (II) are both hydrogen; at least one of R4 and R5 is chlorine, and the other is hydrogen; R6 is hydrogen, chlorine, or methyl.

[0040] In some embodiments, R2 and R3 in formula (I) or formula (II) are both hydrogen; at least one of R4 and R5 is fluorine, and the other is hydrogen; R6 is hydrogen or fluorine.

[0041] In some implementations, R2, R3, and R4 in formula (I) or formula (II) are all hydrogen; one of R5 and R6 is chlorine, and the other is hydrogen.

[0042] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is fluorine.

[0043] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is chlorine.

[0044] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; R2 and R3 are both hydrogen; and at least one of R4, R5 and R6 is fluorine or chlorine.

[0045] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine or chlorine, while the other is hydrogen; and R6 is hydrogen, chlorine, fluorine, or methyl.

[0046] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is chlorine, and the other is hydrogen; R6 is hydrogen, chlorine, or methyl.

[0047] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine, while the other is hydrogen; R6 is hydrogen or fluorine.

[0048] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-pyridin-2-yl; R2, R3 and R4 are all hydrogen; one of R5 and R6 is chlorine and the other is hydrogen.

[0049] In some embodiments, in formula (I) or formula (II), R1 is 5-trifluoromethyl-pyridin-2-yl; R2, R3, R5 and R6 are all hydrogen, and R4 is chlorine; or, R2, R3, R4 and R5 are all hydrogen, and R6 is chlorine; or, R2, R3, R4 and R6 are all hydrogen, and R5 is chlorine; or, R2, R3 and R5 are all hydrogen, and R4 and R6 are all chlorine; or, R2, R3 and R5 are all hydrogen, R4 is chlorine, and R6 is methyl; R2, R3 and R5 are all hydrogen, and R4 and R6 are all fluorine; or, R2, R3, R5 and R6 are all hydrogen, and R4 is fluorine.

[0050] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is fluorine.

[0051] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is chlorine.

[0052] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2 and R3 are both hydrogen; and at least one of R4, R5 and R6 is fluorine or chlorine.

[0053] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine or chlorine, while the other is hydrogen; and R6 is hydrogen, chlorine, fluorine, or methyl.

[0054] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is chlorine and the other is hydrogen; R6 is hydrogen, chlorine or methyl.

[0055] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine, while the other is hydrogen; R6 is hydrogen or fluorine.

[0056] In some embodiments, R1 in formula (I) or formula (II) is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2, R3 and R4 are all hydrogen; one of R5 and R6 is chlorine and the other is hydrogen.

[0057] In some embodiments, in formula (I) or formula (II), R1 is 5-trifluoromethyl-3-chloro-pyridin-2-yl; R2, R3, R5 and R6 are all hydrogen, and R4 is chlorine; or, R2, R3, R4 and R5 are all hydrogen, and R6 is chlorine; or, R2, R3, R4 and R6 are all hydrogen, and R5 is chlorine; or, R2, R3 and R5 are all hydrogen, and R4 and R6 are all chlorine; or, R2, R3, and R5 are all hydrogen, R4 is chlorine, and R6 is methyl; R2, R3 and R5 are all hydrogen, and R4 and R6 are all fluorine; or, R2, R3, R5 and R6 are all hydrogen, and R4 is fluorine.

[0058] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalo-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is fluorine.

[0059] In some embodiments, in formula (I) or formula (II), R1 is 6-chloro-quinoxalo-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is chlorine.

[0060] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl; R2 and R3 are both hydrogen; and at least one of R4, R5 and R6 is fluorine or chlorine.

[0061] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine or chlorine, while the other is hydrogen; and R6 is hydrogen, chlorine, fluorine, or methyl.

[0062] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is chlorine and the other is hydrogen; R6 is hydrogen, chlorine or methyl.

[0063] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine, and the other is hydrogen; R6 is hydrogen or fluorine.

[0064] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-quinoxalin-2-yl; R2, R3 and R4 are all hydrogen; one of R5 and R6 is chlorine and the other is hydrogen.

[0065] In some embodiments, in formula (I) or formula (II), R1 is 6-chloro-quinoxalin-2-yl; R2, R3, R5, and R6 are all hydrogen, and R4 is chlorine; or, R2, R3, R4, and R5 are all hydrogen, and R6 is chlorine; or, R2, R3, R4, and R6 are all hydrogen, and R5 is chlorine; or, R2, R3, and R5 are all hydrogen, and R4 and R6 are all chlorine; or, R2, R3, and R5 are all hydrogen, R4 is chlorine, and R6 is methyl; R2, R3, and R5 are all hydrogen, and R4 and R6 are all fluorine; or, R2, R3, R5, and R6 are all hydrogen, and R4 is fluorine.

[0066] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazole-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is fluorine.

[0067] In some embodiments, in formula (I) or formula (II), R1 is 6-chloro-benzoxazole-2-yl; at least one of the groups R2, R3, R4, R5 and R6 is chlorine.

[0068] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazole-2-yl; R2 and R3 are both hydrogen; and at least one of R4, R5 and R6 is fluorine or chlorine.

[0069] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazole-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine or chlorine, while the other is hydrogen; and R6 is hydrogen, chlorine, fluorine, or methyl.

[0070] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazole-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is chlorine and the other is hydrogen; R6 is hydrogen, chlorine or methyl.

[0071] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazol-2-yl; R2 and R3 are both hydrogen; at least one of R4 and R5 is fluorine, while the other is hydrogen; R6 is hydrogen or fluorine.

[0072] In some embodiments, R1 in formula (I) or formula (II) is 6-chloro-benzoxazol-2-yl; R2, R3 and R4 are all hydrogen; one of R5 and R6 is chlorine and the other is hydrogen.

[0073] In some embodiments, in formula (I) or formula (II), R1 is 6-chloro-benzoxazol-2-yl; R2, R3, R5, and R6 are all hydrogen, and R4 is chlorine; or, R2, R3, R4, and R5 are all hydrogen, and R6 is chlorine; or, R2, R3, R4, and R6 are all hydrogen, and R5 is chlorine; or, R2, R3, and R5 are all hydrogen, and R4 and R6 are all chlorine; or, R2, R3, and R5 are all hydrogen, R4 is chlorine, and R6 is methyl; R2, R3, and R5 are all hydrogen, and R4 and R6 are all fluorine; or, R2, R3, R5, and R6 are all hydrogen, and R4 is fluorine.

[0074] In some preferred embodiments, the novel propyl phenoxypropionate compound is selected from one of the following compounds:

[0075]

[0076]

[0077]

[0078]

[0079] Or its stereoisomers, solvates, hydrates, or pharmaceutically acceptable salts.

[0080] In some preferred embodiments, the novel propyl phenoxypropionate compound is selected from one of the following compounds:

[0081]

[0082]

[0083]

[0084]

[0085] Or its stereoisomers, solvates, hydrates, or pharmaceutically acceptable salts.

[0086] In some preferred embodiments, the novel propyl phenoxypropionate compound is selected from one of the following compounds:

[0087]

[0088]

[0089]

[0090] Secondly, this application provides a method for preparing the compound or its stereoisomer, solvate, hydrate, or pharmaceutically acceptable salt described in the first aspect of this document, including:

[0091] Compound (V) undergoes an esterification reaction with compound (VI) to yield compound (I).

[0092]

[0093] Here, X in formula (V) is a halogen (e.g., chlorine, bromine, or iodine), and the definitions of R1 in formula (V) and R2, R3, R4, R5, and R6 in formula (VI) are the same as the corresponding groups in formula (I).

[0094] In some embodiments of the second aspect, the preparation method further includes:

[0095] (1) The compound of formula (III) undergoes a hydrolysis reaction to obtain the compound of formula (V);

[0096]

[0097] (2) The compound of formula (IV) reacts with a halogenating agent to give the compound of formula (V);

[0098]

[0099] Here, R7 in formula (III) is a C1-C4 alkyl group; X in formula (V) is a halogen, and the definition of R1 in formulas (III) to (V) is the same as the corresponding group in formula (I) above.

[0100] In some embodiments of the second aspect, the esterification reaction can be carried out using conventional esterification methods, for example, the esterification reaction is carried out in an organic solvent such as dichloromethane, in the presence of an organic base such as triethylamine or diisopropylethylamine or pyridine, under ice bath conditions, by adding an organic solution of compound (V) dropwise, monitoring the reaction to completion by TLC, and then obtaining compound (I) by conventional post-treatment.

[0101] In some embodiments of the second aspect, the hydrolysis reaction may be carried out in the presence of an acid catalyst or a base catalyst (e.g., sodium hydroxide).

[0102] In some embodiments of the second aspect, the halogenating agent may be oxalyl chloride, thionyl chloride, or POCl3.

[0103] Thirdly, this application provides a pesticide composition comprising the compound described in the first aspect herein, or a stereoisomer thereof, solvate, hydrate, or pharmaceutically acceptable salt thereof.

[0104] In some embodiments of the third aspect, the pesticide composition further comprises one or more formulation adjuvants.

[0105] In some embodiments of the third aspect, the pesticide composition is formulated as a technical grade, emulsifiable concentrate, powder, granules, suspension concentrate, water emulsion, or aqueous solution; the powder is optionally a wettable powder; the granules are optionally water-dispersible granules; and the suspension concentrate is optionally a dispersible oil suspension.

[0106] In some embodiments of the third aspect, the pesticide composition further includes formulation adjuvants or additives.

[0107] In some embodiments of the third aspect, the pesticide composition comprises at least one additional pesticide-active substance, said additional pesticide-active substance being selected from insecticides, acaricides, herbicides, fungicides, growth regulators, and safeners.

[0108] In some embodiments of the third aspect, the pesticide composition typically contains 0.05-95% (by weight), preferably 0.5-50% (by weight), at least one compound of formula (I).

[0109] The propyl phenoxypropionate compounds of this application, or pesticide compositions containing them, can be applied by spraying, misting, dusting, spreading, or irrigating in the form of directly sprayable aqueous solutions, powders, suspensions, highly concentrated aqueous formulations, oils or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusting compositions, broadcasting compositions, or granules. The method of application depends on the intended use, and in each case, the compounds of this application should be dispersed as uniformly as possible.

[0110] The compounds shown in formula (I) are generally suitable for preparing sprayable solutions, emulsions, ointments, or oil dispersions. Suitable formulation adjuvants or inert additives include: medium to high boiling point mineral oils (such as kerosene or diesel oil and coal tar), vegetable or animal oils, aliphatic hydrocarbons, cyclic hydrocarbons and aromatic hydrocarbons (such as paraffin, tetrahydronaphthalene, tetrahydronaphthalene or its derivatives, alkylbenzene or its derivatives), methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone or strongly polar solvents such as N-methylpyrrolidone or water.

[0111] Aqueous formulations can be prepared by adding water to concentrated emulsions, suspensions, ointments, wettable powders, or water-dispersible particles. To prepare emulsions, ointments, or oil dispersions, raw materials, either directly or dissolved in oil or solvent, can be homogenized in water using a wetting agent, binder, dispersant, or emulsifier. However, concentrates consisting of compounds of formula (I) of this application, wetting agents, binders, dispersants, or emulsifiers can also be prepared, as well as concentrates containing solvents or oils, which are suitable for dilution with water.

[0112] By mixing or grinding the compound of formula (I) of this application with a solid carrier, powder, spreading and dusting compositions can be prepared.

[0113] By incorporating the compound of formula (I) of this application onto a solid carrier, particles such as coated, impregnated, and homogeneous particles can be prepared. The solid carrier may be selected from, for example, mineral soils such as silica, silica gel, silicates, talc, kaolin, limestone, lime, red basalt, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide; ground synthetic materials; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; and plant products such as cereal flour, bark powder, wood material and nut shell powder, cellulose powder; or other solid carriers.

[0114] Preferably, the compound of formula (I) of this application is formulated as an emulsifiable concentrate, and the content of the compound of formula (I) is 0.05-95% by weight, based on the total weight of the emulsifiable concentrate; preferably 0.5-50% by weight.

[0115] The emulsifiable concentrate is preferably formulated by weight of: 2% of compound (I), 20% solvent oil, 8% calcium dodecylbenzenesulfonate, 8% castor oil polyoxyethylene (10) ether, and methyl oleate to make up to 100%.

[0116] Preferably, the solvent oil is selected from aromatic solvent oil, and the amount used is preferably 10-40%, and most preferably 15-30%.

[0117] The compound of formula (I) of this application can also be formulated into an aqueous emulsion, wherein the content of the compound of formula (I) is 1-50% by weight, preferably 2-35% by weight, based on the total weight of the aqueous emulsion.

[0118] The water emulsion formulation is as follows, based on the total weight of the emulsion: 2% of the compound of formula (I), 10% solvent oil, 3% calcium dodecylbenzenesulfonate, 4% nonylphenol polyoxyethylene (10) ether, 5% ethylene glycol, and water to make up to 100%.

[0119] The compound of formula (I) of this application can also be formulated into an oil suspension, wherein the content of the compound of formula (I) is 0.5-80% by weight, preferably 2-35% by weight, based on the total weight of the oil suspension.

[0120] Based on the total weight of the oil suspension, the formulation of the oil suspension is 10% of the compound of formula (I), 5% solvent oil, 7.5% calcium dodecylbenzenesulfonate, 7.5% castor oil polyoxyethylene (10) ether, 1.5% organobentonite, 1% silica, and methyl oleate to make up to 100%.

[0121] This application does not impose any particular restrictions on the methods for forming formulations such as emulsifiable concentrates, water-in-oil emulsions, and oil suspensions. Those skilled in the art can refer to "Modern Pesticide Formulation Processing Technology" for formulation preparation.

[0122] Fourthly, this application provides a method for controlling unwanted plant growth, comprising applying a pesticide-effective amount of at least one compound of the first aspect of this application or the pesticide composition described in the third aspect to the plant to be controlled, plant parts, plant seeds or the location where unwanted plant growth is desired.

[0123] Fifthly, this application provides the use of the compounds of the first aspect or the pesticide compositions described in the third aspect of this application as herbicides.

[0124] In some embodiments of the fourth or fifth aspect, the unwanted plant growth or use as a herbicide is particularly for the control or removal of grassy weeds. They are generally harmless and therefore can be used on broadleaf plants and monocotyledonous plants that do not belong to the grass family. The grassy weeds mentioned are not limited to barnyard grass, barnyard grass, crabgrass, foxtail grass, jointed goatgrass, goosegrass, wild oats, wild millet, thrush, or paspalum.

[0125] In some embodiments of the fourth or fifth aspect, the compound described in the first aspect or the pesticide composition described in the third aspect of this application may be used to control weeds in field crops.

[0126] In the foregoing application of the present invention, the field crop is at least one of corn, wheat, rice, soybean and rapeseed.

[0127] The compound described in the first aspect or the pesticide composition described in the third aspect is a systemic selective foliar herbicide for post-emergence control of common grass weeds in broadleaf crops such as peanuts, soybeans, and vegetables. The technical grade is a light brown to brown solid with a slightly aromatic odor. It can control a variety of common annual grass weeds such as barnyard grass, crabgrass, goosegrass, barnyard grass, wild oats, foxtail grass, wild millet, thrush, and paspalum notoginseng. It has a wide application period and is safe for broadleaf crops and subsequent crops in conventional crop rotation.

[0128] The beneficial effect of this application is that such compounds are generally used in broadleaf fields such as peanut, cotton, and rapeseed fields to control grass weeds, and are rarely applied to grass crops such as wheat, rice, millet, and corn. The compounds discovered in this invention have good selectivity in rice or wheat, which expands the scope of application of such agents and provides a new option for the increasingly serious problem of weed resistance management.

[0129] Other features and advantages of this application will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the application. Other advantages of this application may be realized and obtained by means of the solutions described in the specification. Detailed Implementation

[0130] To make the objectives, technical solutions, and advantages of this application clearer, the embodiments of the present invention will be described in detail below. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be arbitrarily combined with each other.

[0131] Definition of terminology

[0132] "Stereoisomer" refers to the stereoisomers of the propyl phenoxypropionate compounds of this application, such as enantiomers, diastereomers (or epimers). Enantiomers or diastereomers may occur when one or more asymmetric carbon atoms are present. In this application, the propyl phenoxypropionate compounds include all stereoisomers not characterized in a specific stereoisomer form, or mixtures thereof in any proportion.

[0133] "Solvate" refers to a chemically quantifiable composition formed with the propyl phenoxypropionate compound or its salt thereof in this application and a solvent. "Hydrate" is a special form of solvate, such as monohydrate, sesquihydrate, dihydrate, etc.

[0134] "Agrochemically acceptable salts" include those that form acid addition salts with the propyl phenoxypropionate compounds of this application, including but not limited to inorganic acid salts or organic acid salts; the inorganic acids are, for example, HCl, HBr, H2SO4, H3PO4 or HNO3; the organic acids are carboxylic acids (such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid, lactic acid or salicylic acid) or sulfonic acids (such as methanesulfonic acid or p-toluenesulfonic acid).

[0135] "Safeners" are a class of substances that enhance the selectivity of herbicides; known safeners for herbicides include glyphosate, glyphosate nitrile, glyphosate oxychloride, glyphosate oxychloride and pyrazosulfuron-methyl, bis(oxazolyl) acid, cyclopropanesulfonamide, etc.

[0136] Unless otherwise specified in this application, nuclear magnetic resonance (NMR) measurements were performed on an AVANCE III 600 NMR spectrometer (Bruck, Germany). LC-MS measurements were performed using an Agilent 1260-6120.

[0137] Preparation scheme 1

[0138]

[0139] Operating steps:

[0140] (1) Add 500g (1.38mol) of quizalofop-P-ethyl and 2000mL of tetrahydrofuran to a 1000mL reaction flask, stir until completely dissolved, cool to 10℃ and add 80.30g (2.08mol) of sodium hydroxide and 2000mL of water to form a solution, let it rise naturally to room temperature and stir for 6 hours, stop the reaction, add 2000mL of ethyl acetate to the reaction solution, separate the layers, adjust the pH of the aqueous phase to 1-2 with 379g (3.12mol) of concentrated hydrochloric acid, filter, dry the filter cake to obtain 285g of white solid with a purity of 98% and a yield of 35%.

[0141] (2) Add 100g (0.3mol) of intermediate acid and 400mL of dichloromethane to a 500mL three-necked flask, cool to 0-5℃ in an ice-water bath with stirring, and add 45g (0.36mol) of oxalyl chloride dropwise. After the addition is complete, keep the temperature at 20-30℃ for 5-6 hours until the solid is completely dissolved. Continue to keep the temperature at 2 hours and remove the solvent on a rotary evaporator. Add 50mL of dichloromethane to dissolve the solid and then evaporate it to dryness. Remove excess oxalyl chloride as much as possible to obtain 110g of grayish-white solid with a purity of 97%.

[0142] (3) Add 4.3 g (0.0427 mol, 1.5 eq) of triethylamine, 1.2 eq of B (alcohol), and 300 mL of dichloromethane to a 500 mL three-necked flask. Cool the mixture to 0-5 °C in an ice-water bath with stirring. Add 10 g (0.0285 mol, 1 eq) of phenoxypropionyl chloride in 100 mL of dichloromethane solution dropwise. After the addition is complete, keep the mixture at 30-35 °C for 5-6 hours. Monitor the reaction by TLC. Once the reaction is complete, cool the mixture to room temperature and wash twice with 200 mL of water. Extract the aqueous layer once with 100 mL of dichloromethane. Combine the organic layers, dry with anhydrous sodium sulfate, filter, and remove solvent to obtain a pale yellow oily liquid. Purify by column chromatography to obtain 7.5-12.9 g of product with a purity of 95.1%-99.5%.

[0143] Preparation scheme 2

[0144]

[0145] Operating steps:

[0146] (1) Add 372g (1mol) of quizalofop-P-ethyl and 1500mL of tetrahydrofuran to a 1000mL reaction flask, stir until completely dissolved, cool to 10℃ and add 40g (1.0mol) of sodium hydroxide and 1000mL of water to form a solution, let it rise naturally to room temperature and stir for 6 hours, stop the reaction, add 2000mL of ethyl acetate to the reaction solution, adjust the pH of the aqueous phase to 1-2 with 182g (1.5mol) of concentrated hydrochloric acid, separate the layers, dry and concentrate to obtain 207g of intermediate acid with a purity of 98% and a yield of 60%.

[0147] (2) Add 34g (0.1mol) phenoxypropionic acid and 100mL dichloromethane to a 500mL three-necked flask, cool to 0-5℃ in an ice-water bath with stirring, add 15g (0.12mol) oxalyl chloride dropwise, and after the addition is complete, keep the temperature at 20-30℃ for 2 hours until the solid is completely dissolved. Continue to keep the temperature at 2 hours and remove the solvent on a rotary evaporator. Add 20mL of dichloromethane to dissolve, and then evaporate to dryness. Try to remove excess oxalyl chloride to obtain 35g of pale yellow solid with a purity of 97%.

[0148] (3) Add 4.3 g of triethylamine (0.0427 mol 1.5 eq), 1.2 eq of B (alcohol) and 300 mL of dichloromethane to a 500 mL three-necked flask, and cool to 0-5 °C in an ice-water bath with stirring. Add 10 g of acyl chloride (1 eq of 0.0275 mol in 100 mL of dichloromethane solution) dropwise. After the addition is complete, keep the reaction at 30-35 °C for 5-6 hours and monitor with TLC. After the reaction is complete, cool to room temperature, wash twice with 200 mL of water, extract the aqueous layer once with 100 mL of dichloromethane, combine the organic layers, dry with anhydrous sodium sulfate, filter, and desolvent to obtain a pale yellow oily liquid. Purify by column chromatography to obtain 9.2-13.8 g of product with a purity of 96.7%-99%.

[0149] Preparation scheme three

[0150]

[0151] Operating steps:

[0152] (1) Add 375g (1mol) of high-efficiency flupyradifurone and 1500mL of tetrahydrofuran to a 1000mL reaction flask, stir until completely dissolved, cool to 10℃ and add 40g (1.0mol) of sodium hydroxide and 1000mL of water to form a solution, let it rise naturally to room temperature and stir for 6 hours, stop the reaction, add 2000mL of ethyl acetate to the reaction solution, adjust the pH of the aqueous phase to 1-2 with 182g (1.5mol) of concentrated hydrochloric acid, separate the layers, dry and concentrate to obtain 235g of intermediate acid with a purity of 98% and a yield of 65%.

[0153] (2) Add 36g (0.1mol) of phenoxypropionic acid and 100mL of dichloromethane to a 500mL three-necked flask, cool to 0-5℃ in an ice-water bath with stirring, add 15g (0.12mol) of oxaloyl chloride dropwise, and after the addition is complete, keep the temperature at 20-30℃ for 2 hours until the solid is completely dissolved. Continue to keep the temperature at 2 hours and remove the solvent on a rotary evaporator. Add 20mL of dichloromethane to dissolve, and then evaporate to dryness. Try to remove excess oxaloyl chloride to obtain 34g of pale yellow solid with a purity of 97%.

[0154] (3) Add 4.3 g of triethylamine (0.0427 mol 1.5 eq), 1.2 eq of B (alcohol) and 300 mL of dichloromethane to a 500 mL three-necked flask, and cool to 0-5 °C in an ice-water bath with stirring. Add 10 g of acyl chloride (1 eq of 0.0263 mol in 100 mL of dichloromethane solution) dropwise. After the addition is complete, keep the temperature at 30-35 °C for 5-6 hours. Monitor the reaction by TLC. After the reaction is complete, cool to room temperature, wash twice with 200 mL of water, and extract the aqueous layer once with 100 mL of dichloromethane. Combine the organic layers, dry with anhydrous sodium sulfate, filter, and desolvent to obtain a pale yellow oily liquid. Purify by column chromatography to obtain 8.0-11.9 g of product with a purity of 99.5%-99%.

[0155] Preparation scheme four

[0156]

[0157] Operating steps

[0158] (1) Add 383g (1mol) of quizalofop-P-ethyl and 1500mL of tetrahydrofuran to a 1000mL reaction flask, stir until completely dissolved, cool to 10℃ and add 40g (1.0mol) of sodium hydroxide and 1000mL of water to form a solution, let it rise naturally to room temperature and stir for 6 hours, stop the reaction, add 2000mL of ethyl acetate to the reaction solution, adjust the pH of the aqueous phase to 1-2 with 182g (1.5mol) of concentrated hydrochloric acid, separate the layers, dry and concentrate to obtain 215g of intermediate acid with a purity of 98% and a yield of 64.4%.

[0159] (2) Add 32g (0.1mol) phenoxypropionic acid and 100mL dichloromethane to a 500mL three-necked flask, cool to 0-5℃ in an ice-water bath with stirring, add 15g (0.12mol) oxalyl chloride dropwise, and after the addition is complete, keep the temperature at 20-30℃ for 2 hours until the solid is completely dissolved. Continue to keep the temperature at 2 hours and remove the solvent on a rotary evaporator. Add 20mL dichloromethane to dissolve, and then evaporate to dryness. Try to remove excess oxalyl chloride to obtain 30g of pale yellow solid with a purity of 97%.

[0160] (3) Add 4.3 g of triethylamine (0.0427 mol 1.5 eq), 1.2 eq of alcohol B, and 300 mL of dichloromethane to a 500 mL three-necked flask. Cool to 0-5 °C in an ice-water bath with stirring. Add dropwise (10 g of acyl chloride and 1 eq of 0.0275 mol of 100 mL dichloromethane solution). After the addition is complete, keep the mixture at 30-35 °C for 5-6 hours. Monitor the reaction by TLC. After the reaction is complete, cool to room temperature and wash twice with 200 mL of water. Extract the aqueous layer once with 100 mL of dichloromethane. Combine the organic layers, dry with anhydrous sodium sulfate, filter, and remove the solvent to obtain a pale yellow oily liquid. Purify by column chromatography to obtain 8.5 g-12.2 g of product with a purity of 96.5%-98.4%.

[0161] Examples 1 to 9

[0162] Compounds B01, B08, B02, B03, B04, B05, B06, B09, and B07 were prepared using the method described in Preparation Scheme 1.

[0163] Compound BA21230 is also known as compound B01

[0164]

[0165] The yield was 56.9%. 1 H NMR (600MHz, CDCl3) δ7.43-7.30(m,3H),7.18(d,4H),6.94-6.85(m,4H),4.75( t,1H),4.58(t,1H),4.45-4.38(m,1H),4.29(d,1H),1.60(d,3H),1.33(d,3H).

[0166] Compound BA21231 is also known as compound B08.

[0167]

[0168] The yield was 63.8%. 1 H NMR (600MHz, CDCl3) δ7.45-7.34(m,2H),7.23-7.11(m,4H),6.91-6.86(m,4H),6.83-6.70(m,1H),4.80-4. 68(m,1H),4.60-4.50(m,1H),4.49-4.39(m,1H),4.35-4.28(m,1H),1.64-1.53(m,3H),1.31-1.26(m,3H).

[0169] Compound BA21232 is also known as compound B02

[0170]

[0171] The yield was 71.5%. 1 H NMR (600MHz, CDCl3) δ7.65-7.47(m,2H),7.45-7.24(m,4H),6.99-6.77(m,4H),4.88-4.68(m, 1H),4.60-4.50(m,1H),4.41-4.32(m,1H),4.21-4.11(m,1H),1.77-1.46(m,3H),1.39(d,3H).

[0172] Compound BA21233 is also known as compound B03.

[0173]

[0174] The yield was 68.3%. 1 H NMR (600MHz, CDCl3) δ7.72-7.54(m,2H),7.51-7.34(m,4H),7.22-6.871(m,4H),4.96-4.79(m,1H),4. 710-4.603(m,1H),4.55-4.42(m,1H),4.20-4.11(m,1H),1.85(d,3H)1.80-1.55(m,3H),1.38(d,3H).

[0175] Compound BA21234 is also known as compound B04.

[0176]

[0177] The yield was 55.7%. 1 H NMR (600MHz, CDCl3) δ7.75-7.57(m,3H),7.55-7.32(m,4H),7.25-7.16(m,3H),4.98-4.77(m, 1H),4.63-4.54(m,1H),4.51-4.43(m,1H),4.35-4.17(m,1H),1.87-1.69(m,3H),1.44(d,3H).

[0178] Compound BA21235 is also known as compound B05.

[0179]

[0180] The yield was 63.7%. 1H NMR (600MHz, CDCl3) δ7.50-7.35(m,2H),7.26-7.19(m,3H),6.99-6.87(m,4H),6.86-6.79(m,2H),4. 75(d,1H),4.49(d,1H),4.39-4.31(m,1H),4.28-4.20(m,1H),1.64-1.60(m,3H),1.31-1.25(m,3H).

[0181] Compound B06

[0182]

[0183] The yield was 62.5%. 1 H NMR (600MHz, CDCl3) δ7.52-7.35(m,2H),7.34-7.15(m,5H),7.02-6.69(m,4H),4.86-4. 67(m,1H),4.64-4.50(m,1H),4.44-4.13(m,2H),1.70-1.49(m,3H),1.34-1.26(m,3H).

[0184] Compound BA21250 is also known as compound B09.

[0185]

[0186] The yield was 65.8%. 1 H NMR (600MHz, CDCl3) δ7.55-7.37(m,2H),7.36-7.14(m,5H),7.04-6.71(m,4H),4.88-4. 68(m,1H),4.65-4.50(m,1H),4.46-4.15(m,2H),1.73-1.51(m,3H),1.36-1.28(m,3H).

[0187] Compound BA21251 is also known as compound B07.

[0188]

[0189] The yield was 68.4%. 1H NMR(600MHz, CDCl3)δ7.43(d,2H),7.33-7.16(m,5H),7.04-6.88(m,2H),6.84(t,2H),4.77(d, 1H),4.60-4.50(m,1H),4.40(d,1H),4.32-4.19(m,1H),1.86-1.54(m,3H),1.44-1.20(m,3H).

[0190] Examples 10 to 16

[0191] Compounds B32, B33, B27, B28, B29, B30, and B31 were prepared using method four.

[0192] Compound BA21252 is also known as compound B32.

[0193]

[0194] The yield was 75.2%. 1 H NMR(600MHz, CDCl3)δ8.35(d,1H),8.02(d,1H),7.24-7.14(m,2H),7.08-6.93(m,2H),6.93-6.83(m,3H),6. 80-6.72(m,2H),4.75(d,1H),4.52(d,1H),4.45-4.31(m,1H),4.25(d,1H),1.62-1.58(m,3H),1.38(d,3H).

[0195] Compound BA21253 is also known as compound B33.

[0196]

[0197] The yield was 66.7%. 1 H NMR(600MHz, CDCl3)δ8.32(s,1H),7.79(d,1H),7.25(d,1H),7.19-7.13(m,2H),7.04-6.93(m,3H),6.82-6.75(m, 3H),4.85(d,1H),4.69-4.59(m,1H),4.45-4.37(m,1H),4.35-4.29(m,1H),1.65-1.59(m,3H),1.37-1.32(m,3H).

[0198] Compound BA21254 is also known as compound B27.

[0199]

[0200] The yield was 63.4%. 1 H NMR(600MHz, CDCl3)δ8.44(d,1H),8.16(d,1H),7.18-7.12(m,2H),6.97-6.88(m,3H),6.94( d,2H),6.76(d,2H),4.87(d,1H),4.59(d,1H),4.37-4.26(m,2H),1.67(d,3H),1.305(d,3H).

[0201] Compound BA21255 is also known as compound B28.

[0202]

[0203] The yield was 58.9%. 1 H NMR(600MHz, CDCl3)δ8.42(s,1H),7.87(d,1H),7.37(d,1H),7.16-7.09(m,1H),7.04-6.93(m,3H),6.91-6.80(m, 3H),4.75(d,1H),4.59-4.49(m,1H),4.45-4.34(m,1H),4.33-4.22(m,1H),1.65-1.59(m,3H),1.37-1.30(m,3H).

[0204] Compound BA21256 is also known as compound B29.

[0205]

[0206] The yield was 69.4%. 1 H NMR(600MHz, CDCl3)δ8.41(s,1H),7.87(d,1H),7.14-7.02(m,2H),7.00-6.91(m,3H),6.90-6.82(m,2H),6.73(d, 1H),4.73(d,1H),4.56-4.47(m,1H),4.43-4.33(m,1H),4.26(d,1H),2.20-2.06(m,3H),1.60(d,3H),1.29(d,3H).

[0207] Compound BA21257 is also known as compound B30.

[0208]

[0209] The yield was 72.3%. 1H NMR(600MHz, CDCl3)δ8.67(d,1H),8.04(d,1H),7.72-7.55(m,2H),7.24-7.02(m,3H),6.95-6.75(m,3 H),4.77(d,1H),4.60-4.47(m,1H),4.36(d,1H),4.27(d,,1H),1.72-1.55(m,3H),1.32-1.19(m,3H).

[0210] Compound BA21258 is also known as compound B31.

[0211]

[0212] The yield was 61.7%. 1 H NMR(600MHz, CDCl3)δ8.54(d,,1H),8.16(d,2H),7.10-6.97(m,2H),6.96-6.71(m,6H),4.77 (d,1H),4.44(t,1H),4.36-4.31(m,1H),4.31-4.27(m,1H),1.62(t,3H),1.33-1.27(m,3H).

[0213] Examples 17 to 23

[0214] Compounds B11, B12, B13, B14, B15, B16 and B17 were prepared using preparation scheme two.

[0215] Compound BA21236 is also known as compound B11

[0216]

[0217] The yield was 71.9%. 1 H NMR(600MHz, CDCl3)δ8.71(d,1H),8.13(d,1H),7.90-7.75(m,2H),7.41-6.92(m,4H),6.84-6.61(m,4H),4 .93-4.85(m,1H),4.75-4.56(m,1H),4.53-4.45(m,1H),4.37(d,1H),1.69-1.59(m,3H),1.39-1.30(m,3H).

[0218] Compound BA21237 is also known as compound B12.

[0219]

[0220] The yield was 69.9%. 1 H NMR(600MHz, CDCl3)δ8.51(d,1H),7.94(d,1H),7.62-7.45(m,2H),7.12-6.93(m,4H),6.80-6.61(m,4H),4 .72-4.65(m,1H),4.51-4.36(m,1H),4.31-4.20(m,1H),4.15(d,1H),1.61-1.49(m,3H),1.39-1.16(m,3H).

[0221] Compound BA21238 is also known as compound B13.

[0222]

[0223] The yield was 62.4%. 1 H NMR(600MHz, CDCl3)δ8.66(d,1H),8.05(d,1H),7.70-7.56(m,2H),7.35(d,1H),7.19-7.02(m,3H),6.95-6.81 (m,3H),4.99-4.78(m,1H),4.61-4.51(m,1H),4.43(d,1H),4.33-4.25(m,1H),1.69-1.60(m,3H),1.34(d,3H).

[0224] Compound BA21239 is also known as compound B14.

[0225]

[0226] The yield was 72.3%. 1 H NMR(600MHz, CDCl3)δ8.56(d,1H),8.04(d,1H),7.81-7.66(m,2H),7.35-7.11(m,3H),6.83-6.62(m,4H),4.91-4.82 (m,1H),4.65-4.49(m,1H),4.41-4.32(m,1H),4.27(d,1H),1.95-1.72(m,3H),1.55-1.49(m,3H),1.35-1.29(m,3H).

[0227] Compound BA21240 is also known as compound B15.

[0228]

[0229] The yield was 66.7%. 1H NMR(600MHz, CDCl3)δ8.95(d,1H),8.55(d,1H),7.99-7.79(m,2H),7.67(d,1H),7.49-7.31(m,3H),6.85-6.75 (m,3H),4.69-4.58(m,1H),4.55-4.50(m,1H),4.48(d,1H),4.43-4.35(m,1H),1.59-1.65(m,3H),1.39(d,3H).

[0230] Compound BA21241 is also known as compound B16.

[0231]

[0232] The yield was 68.8%. 1 H NMR(600MHz, CDCl3)δ8.85(d,1H),8.29(d,1H),7.91-7.79(m,2H),7.46-7.00(m,4H),6.95-6.71(m,4H),4 .92-4.83(m,1H),4.81-4.59(m,1H),4.51-4.43(m,1H),4.35(d,1H),1.75-1.69(m,3H),1.35-1.29(m,3H).

[0233] Compound BA21242 is also known as compound B17.

[0234]

[0235] The yield was 65.4%. 1 H NMR(600MHz, CDCl3)δ8.67(d,1H),8.04(d,1H),7.71-7.56(m,2H),7.24-7.00(m,4H),6.93-6.72(m,4H),4 .81-4.72(m,1H),4.60-4.49(m,1H),4.41-4.32(m,1H),4.27(d,1H),1.65-1.59(m,3H),1.33-1.26(m,3H).

[0236] Examples 25 to 31

[0237] Compounds B25, B19, B20, B21, B22, B23, and B24 were prepared using method three.

[0238] Compound BA21243 is also known as compound B25.

[0239]

[0240] The yield was 74.3%. 1 H NMR (600MHz, CDCl3) δ8.24(d,1H),7.96(d,1H),7.24-7.14(m,2H),7.08-6.93(m,2H),6.93-6.83(m,2H),6. 80-6.72(m,2H),4.75(d,1H),4.52(d,1H),4.40-4.31(m,1H),4.25(d,1H),1.62-1.58(m,3H),1.28(d,3H).

[0241] Compound BA21244 is also known as compound B19.

[0242]

[0243] The yield was 71.1%. 1 H NMR(600MHz, CDCl3)δ8.34(d,1H),7.99(d,1H),7.64-7.56(m,2H),7.21-6.89(m,6H),4. 87(d,1H),4.63(d,1H),4.50-4.45(m,1H),4.35(d,1H),1.69-1.59(m,3H),1.39(d,3H).

[0244] Compound BA21245 is also known as compound B20.

[0245]

[0246] The yield was 63.5%. 1 H NMR (600MHz, CDCl3) δ8.36(d,1H),8.15(d,1H),7.36-7.21(m,2H),7.15-6.99(m,2H),6.93-6.81(m,2H),6. 73-6.62(m,2H),4.84(d,1H),4.65(d,1H),4.49-4.29(m,1H),4.11(d,1H),1.79-1.68(m,3H),1.35(d,3H).

[0247] Compound BA21246 is also known as compound B21

[0248]

[0249] The yield was 66.7%. 1H NMR(600MHz, CDCl3)δ8.15(d,1H),7.80(d,1H),6.90-6.80(m,2H),6.75-6.60(m,3H),6.54( d,1H),6.46(d,1H),4.67(d,1H),4.39(d,1H),4.27-4.18(m,2H),1.62(d,3H),1.33(d,3H).

[0250] Compound BA21247 is also known as compound B22.

[0251]

[0252] The yield was 70.5%. 1 H NMR (600MHz, CDCl3) δ8.24(d,1H),7.96(d,1H),7.24-7.14(m,2H),7.08-6.99(m,2H),6.93-6.85(m,2H),6.70-6.62( m,1H),4.75(d,1H),4.52(d,1H),4.45-4.39(m,1H),4.35(d,1H),1.72-1.65(m,3H),1.65-1.55(m,3H),1.38(d,3H).

[0253] Compound BA21248 is also known as compound B23.

[0254]

[0255] The yield was 64.3%. 1 H NMR (600MHz, CDCl3) δ8.24(d,1H),7.96(d,1H),7.08-6.99(m,2H),6.97-6.88(m,3H),6.84( d,1H),6.76(d,1H),4.77(d,1H),4.44(d,1H),4.37-4.26(m,2H),1.62(d,3H),1.30(d,3H).

[0256] Compound BA21249 is also known as compound B24.

[0257]

[0258] The yield was 61.4%. 1H NMR(600MHz, CDCl3)δ8.54(d,1H),8.21(d,1H),7.54-7.30(m,2H),7.20-6.89(m,6H),4. 97(d,1H),4.75(d,1H),4.61-4.53(m,1H),4.49(d,1H),1.79-1.65(m,3H),1.45(d,3H).

[0259] Test case

[0260] The following are some preferred application examples of the herbicide of the present invention.

[0261] The herbicide of the present invention is in the form of an emulsifiable concentrate. Based on the total weight of the emulsifiable concentrate, compounds B01-30 are all formulated into 2% emulsifiable concentrates.

[0262]

[0263] The solvent oil, model S200, was produced by Mobil AG; calcium dodecylbenzenesulfonate, also known as Agricultural Emulsion No. 500, was purchased from Shandong Tiandao Company; castor oil polyoxyethylene (10) ether, model BY110, was purchased from Shandong Tiandao Company; methyl oleate was purchased from Yihai Kerry Company. Quizalofop-P-ethyl and quizalofop-P-ethyl were purchased from Jingbo Agricultural Chemical Technology Co., Ltd.; high-efficiency flupyridine haloxyfop-P-ethyl was purchased from Shandong Lvba Chemical Co., Ltd.; and quizalofop-P-ethyl was purchased from Shandong Binnong Technology Co., Ltd.

[0264] Preparation method: Taking 100g of emulsifiable concentrate and compound B01 as an example, first weigh 20g of solvent oil into a beaker, add 2.12g of compound B01 (94% content), stir until transparent, then add 8g of calcium dodecylbenzenesulfonate, 8g of castor oil polyoxyethylene (10) ether, and 61.88g of methyl oleate. Stir until a homogeneous and transparent liquid is formed, which is an emulsifiable concentrate containing 2% compound B01.

[0265] The inventors also formulated compounds B1-33 of this application according to application example 1 and conducted indoor stem and leaf activity tests.

[0266] Test reagent: 2% emulsifiable concentrate of compound B1

[0267] The dosages for treating barnyard grass, crabgrass, and *Echinochloa crus-galli* are: 22.5, 45, and 90 g.ai / ha, respectively.

[0268] Test crops: rice, wheat

[0269] The dosage for the tested crops was 90 and 180 g.ai / ha.

[0270] The equivalent dosage per mu (6.067 hectares) is calculated as the standard dosage of the active ingredient.

[0271] Herbicidal activity test method: The foliar spray method (NY / T 1155.4-2006) was adopted. A certain amount of soil was filled to 3 / 4 of the pot in a transparent plastic cup with a height of 6 cm and a mouth diameter of 4.5 cm. 15 to 20 seeds of the test weeds were evenly sown on the soil surface of the pot. After covering with about 1 cm of fine soil, the pot was placed in a greenhouse (temperature of 22 to 28℃, humidity of 97%) for cultivation.

[0272] When the weeds have grown to the 3-5 leaf stage, perform foliar spraying:

[0273] Barnyard grass: Dilute 2% emulsifiable concentrate with water at 400, 200, and 100 times respectively, and spray at a rate of 30 kg / 667m². 2 Spraying was carried out, with an actual spray area of ​​1m. 2 The diluent used is 45 mL.

[0274] Qianjinzi: Dilute the 2% emulsifiable concentrate with water 400 times and 200 times respectively, and spray at a rate of 30 kg / 667m. 2 Spraying was carried out, with an actual spray area of ​​1m. 2 The diluent used is 45 mL.

[0275] Each treatment was repeated three times, with a control group consisting of a treatment without the herbicide. After treatment, the test materials were placed in a greenhouse for cultivation, and the growth of the target weeds was observed regularly.

[0276] Investigation Methods: After 15 days of experimental treatment, the symptoms of damage and growth inhibition of the target plants were visually observed, and the fresh weight of the aboveground parts was measured. The fresh weight inhibition rate (%) was calculated. Fresh weight inhibition rate (%) = (Control fresh weight - Treatment fresh weight) / Control fresh weight × 100

[0277] Control efficacy (%): Control efficacy (%) = (Number of control plants - Number of surviving plants in treatment) / Number of control plants × 100 Experimental results:

[0278] Tables 1 to 12: Herbicidal activity and safety of the compounds of the present invention.

[0279] Table 1. *Euphorbia lathyris* (compounds B01-B09 of this invention)

[0280]

[0281] Table 2. Barnyard grass (compounds B01-B09 of this invention)

[0282]

[0283]

[0284] Table 3 Safety (Compounds B01-B09 of this invention)

[0285]

[0286] Results analysis: Compared with the control herbicide quizalofop-p-ethyl, compounds B01-B09 showed similar safety in wheat, all being relatively safe, and generally exhibited higher activity against barnyard grass and Echinochloa crus-galli than the control. In rice, except for B08, all compounds showed good safety and generally higher activity. B01 and B02 showed particularly outstanding effects.

[0287] Table 4. Barnyard grass (compounds B11-B17 of this invention)

[0288]

[0289]

[0290] Table 5. Crataegus pinnatifida (compounds B11-B17 of this invention)

[0291]

[0292]

[0293] Table 6 Safety (Compounds B11-B17 of this invention)

[0294]

[0295] Results analysis: Compared with the control herbicide quizalofop-P-ethyl, the safety of the invented compounds B11-B17 in rice was generally poor. Only B13 met the safety requirements and its activity against barnyardgrass was among the top, comparable to quizalofop-P-ethyl. Quizalofop-P-ethyl showed moderate phytotoxicity, which did not meet the requirements. The safety of B11-B17 and the control herbicide quizalofop-P-ethyl in wheat was generally very poor.

[0296] Table 7. Barnyard grass (compounds B19-B25 of this invention)

[0297]

[0298] Table 8. Crataegus pinnatifida (compounds B19-B25 of this invention)

[0299]

[0300] Table 9 Safety (Compounds B19-B25 of this invention)

[0301]

[0302]

[0303] Results analysis: Compared with the control compound haloxyfop-R-methyl, compounds B25, B22, B21, and B20 showed better safety in rice and were more effective than the control compound B25. However, severe phytotoxicity was commonly observed in wheat.

[0304] Table 10 Barnyard grass (compounds B27-B33 of this invention)

[0305]

[0306]

[0307] Table 11. Crataegus pinnatifida (compounds B27-B33 of this invention)

[0308]

[0309]

[0310] Table 12 Safety (Compounds B27-B33 of this invention)

[0311]

[0312] Results analysis: Compared with the control herbicide quizalofop-p-ethyl, compounds B29 and B28 showed better safety in rice, with B29 showing slightly better efficacy against barnyardgrass and crabgrass. Compounds B28 and B29 showed better safety in wheat.

[0313] This application describes several embodiments, but these descriptions are exemplary and not restrictive, and it will be apparent to those skilled in the art that many more embodiments and implementations are possible within the scope of the embodiments described herein. Although discussed in the detailed description, many other combinations of the disclosed features are also possible. Unless specifically limited, any feature of any embodiment may be used in combination with any other feature in any other embodiment, or may substitute for any other feature in any other embodiment.

Claims

1. A propyl phenoxypropionate compound, said propyl phenoxypropionate compound, as shown in formula (I), or a stereoisomer thereof or a pharmaceutically acceptable salt thereof: In formula (I), R1 is 6-chloro-benzoxazole-2-yl; R6 is a halogen, and R2, R3, R4, and R5 are hydrogen; or R3 is a halogen, and R2, R4, R5, and R6 are hydrogen; or R6 is a halogen or an unsubstituted C1-C4 alkyl group, R4 is a halogen, and R2, R3, and R5 are hydrogen; or R4 is a halogen, and R2, R3, R5, and R6 are hydrogen.

2. The compound according to claim 1, wherein, Compound (I) is a compound of formula (II): The definitions of each substituent in formula (II) are the same as those of the corresponding groups in formula (I) of claim 1.

3. The compound according to claim 1 or 2, wherein, The unsubstituted C1-C4 alkyl group is methyl.

4. The compound according to claim 1, wherein, The halogen is fluorine or chlorine.

5. A compound, said compound being selected from one of the following compounds: Or its stereoisomers or pharmaceutically acceptable salts.

6. The compound according to claim 5, wherein, The compound is selected from one of the following compounds: ， Or its stereoisomers or pharmaceutically acceptable salts.

7. A compound, said compound being selected from one of the following compounds: 。 8. A method for preparing the compound according to any one of claims 1-7, comprising: Compound (V) undergoes an esterification reaction with compound (VI) to yield compound (I). ； Here, X in formula (V) is a halogen, and the definitions of R1 in formula (V) and R2, R3, R4, R5 and R6 in formula (VI) are the same as the corresponding groups in the compounds of any one of claims 1-7.

9. The preparation method according to claim 8, wherein, The preparation method further includes: (1) The compound of formula (III) undergoes a hydrolysis reaction to obtain the compound of formula (V); (2) The compound of formula (IV) reacts with a halogenating agent to give the compound of formula (V); Here, R7 in formula (III) is a C1-C4 alkyl group; X in formula (V) is a halogen, and the definitions of R1 in formulas (III) to (V) are the same as the corresponding groups in claim 8.

10. A pesticide composition comprising a pesticide-effective amount of at least one compound of any one of claims 1-7, or a stereoisomer thereof or a pharmaceutically acceptable salt thereof.

11. The pesticide composition according to claim 10, wherein the formulation is a technical grade pesticide, emulsifiable concentrate, powder, granule, suspension concentrate, water emulsion, or aqueous solution.

12. The pesticide composition according to claim 11, wherein the powder is a wettable powder, the granules are water-dispersible granules, and the suspension is a dispersible oil suspension.

13. The pesticide composition according to claim 10 further includes formulation adjuvants or additives.

14. The pesticide composition according to any one of claims 10 to 13, comprising at least one additional pesticide active substance, said additional pesticide active substance being selected from insecticides, acaricides, herbicides, fungicides, growth regulators, and safeners.

15. A method for controlling unwanted plant growth, comprising applying a pesticide-effective amount of at least one compound of any one of claims 1-7 or a pesticide composition of any one of claims 10-14 to the plant to be controlled, plant part, plant seed or location where unwanted plant growth is desired.

16. The use of the compound of any one of claims 1-7, or the pesticide composition of any one of claims 10-14, as a herbicide.

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