CN109232442B - Aryl uracil compound or agriculturally and pharmaceutically acceptable salt thereof, preparation method thereof and herbicide composition - Google Patents
Aryl uracil compound or agriculturally and pharmaceutically acceptable salt thereof, preparation method thereof and herbicide composition Download PDFInfo
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- CN109232442B CN109232442B CN201811067016.9A CN201811067016A CN109232442B CN 109232442 B CN109232442 B CN 109232442B CN 201811067016 A CN201811067016 A CN 201811067016A CN 109232442 B CN109232442 B CN 109232442B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Pest Control & Pesticides (AREA)
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Abstract
The invention provides a phenyl uracil compound shown as a formula I or an agriculturally and pharmaceutically acceptable salt thereof: wherein R is1、R2Independently selected from hydrogen, amino, C1‑C4Alkyl or C1‑C4A haloalkyl group of (a); x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1‑C4Alkyl or substituted C1‑C4Alkyl groups of (a); r3Selected from hydrogen, cyano or C1‑C4Alkyl groups of (a); r4Selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted five-membered or six-membered aromatic heterocyclic group or substituent shown as formula II; wherein R is5Selected from halogens; r6、R7Independently selected from hydrogen, halogen, C1‑C4Alkyl or C1‑C4A haloalkyl group of (a). The compound has the characteristics of wide herbicidal spectrum and high herbicidal activity. The invention also provides a preparation method of the aryl uracil compound or the agriculturally and pharmaceutically acceptable salt thereof and a herbicide composition.
Description
Technical Field
The invention relates to the technical field of organic compounds, in particular to an aryl uracil compound or an agriculturally and pharmaceutically acceptable salt thereof, a preparation method thereof and a herbicide composition.
Background
Because of competing for light and fertilizer water with crops, weeds cause great loss to crop production every year, and the existing method for preventing and controlling weeds mainly sprays pesticides. With the wide application of herbicides such as glyphosate, a large number of weeds have resistance, and in particular, goosegrass has resistance to glyphosate in southern plantations in China, so that the weeds become dominant weeds and malignant weeds. In recent years, some novel phenyluracil herbicides have been proposed, but these herbicides have disadvantages such as poor weed control effect and a narrow weed control range.
Therefore, there is a need for a novel compound having a broad herbicidal spectrum and being less likely to cause resistance to weeds.
Disclosure of Invention
Based on the technical problems, the invention provides an aryl uracil compound or an agriculturally and pharmaceutically acceptable salt thereof, a preparation method thereof and a herbicide composition.
In a first aspect, the present invention provides a phenyluracil compound represented by formula i:
wherein R is1、R2Independently selected from hydrogen, amino, C1-C4Alkyl or C1-C4A haloalkyl group of (a);
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-C4Alkyl or substituted C1-C4Alkyl groups of (a);
R3selected from hydrogen, cyano or C1-C4Alkyl groups of (a);
R4is selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II, wherein the aromatic heterocyclic group comprises aromatic five-membered heterocyclic group or aromatic six-membered heterocyclic group:
in the substituent group shown as the formula II, R5Selected from halogens; r6、R7Independently selected from hydrogen, halogen, C1-C4Alkyl or C1-C4A haloalkyl group of (a).
Alternatively, the agriculturally pharmaceutically acceptable salt of the aryl uracil compound may include, but is not limited to, a sodium salt of the aryl uracil compound, a potassium salt of the aryl uracil compound, an ammonium salt of the aryl uracil compound or the aryl uracil compound. The agriculturally and pharmaceutically acceptable salts of the aryl uracil compounds also include other forms of salts. When the aryl uracil compound is weakly acidic, the aryl uracil compound may form an agriculturally pharmaceutically acceptable salt between cations. The agriculturally and pharmaceutically acceptable salts of the aryl uracil compounds do not have great influence on the functional properties of the aryl uracil compounds.
Alternatively, the aromatic heterocyclic group comprises pyrimidinyl, pyridinyl, pyridazinyl, pyrazinyl, pyranyl, pyrazolyl, imidazolyl, thienyl, furanyl, pyrrolyl, thiazolyl, oxazolyl, or isoxazolyl. Further, optionally, the aromatic heterocyclic group includes at least one heteroatom such as oxygen, nitrogen or sulfur. The aromatic heterocyclic group is bonded through a carbon atom in the aromatic heterocyclic group.
Alternatively, said substituted phenyl or said substituted aromaticThe heterocyclic groups are each substituted with at least one group selected from: alkylamino, amino, halogen, nitro, carboxyl, alkoxycarbonyl, cyano, alkyl, alkoxy or haloalkyl. Further, optionally, the alkylamino group comprises C1-C4Alkyl-substituted amino group of (1). Alternatively, the alkoxycarbonyl group comprises C1-C4Alkoxy-substituted carbonyl of (a). For example, the alkoxycarbonyl group can include, but is not limited to, the group-COOCH3、-COOC2H5or-COOC3H7. Alternatively, the alkyl group comprises C1-C4Alkyl group of (1). Alternatively, the alkoxy group comprises C1-C4Alkoxy group of (2). Alternatively, the haloalkyl group comprises C1-C4Halogen-substituted alkyl of (1).
Alternatively, said substituted phenyl group or said substituted aromatic heterocyclic group is substituted with at least one group selected from: the substituted phenyl group or the substituted aromatic heterocyclic group may have at least one substituent, but the substituted phenyl group or the substituted aromatic heterocyclic group may have 1 or more substituents. Further, optionally, 1-2 substituents are included on the substituted phenyl or the substituted aromatic heterocyclic group. When the substituted phenyl group or the substituted aromatic heterocyclic group includes 2 substituents, the 2 substituents may be the same or different. Further, optionally, the substituted phenyl or the substituted aromatic heterocyclyl substituent includes a variety of position options, including, for example, ortho, meta, or para. For example, the phenyl group substituted with a nitro group includes a 2-nitrophenyl group, a 3-nitrophenyl group or a 4-nitrophenyl group.
Alternatively, the R is4Selected from the group consisting of cyano, nitro, phenyl, cyanophenyl, nitrophenyl, dimethylaminophenyl, dimethoxyphenyl, trifluoromethylphenyl, methylcarbonylphenyl, methylphenyl, phenyl substituted with 1-2 fluorines, phenyl substituted with 1-2 chlorines, pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, pyranyl, pyrazolyl, imidazolyl substituted with 1-2 methyl groups, thienyl, furyl, pyrrolyl, thiazolyl, isoxazolylAn oxazolyl group, an isoxazolyl group substituted with 1-2 methyl groups, an oxazolyl group, or a substituent represented by formula II;
wherein, R is5Selected from fluorine, chlorine or bromine, said R6Selected from hydrogen, fluorine, chlorine, bromine, methyl substituted by 1-3 fluorine, methyl substituted by 1-3 chlorine, ethyl substituted by 1-5 fluorine or ethyl substituted by 1-5 chlorine, R7Selected from fluorine, chlorine, bromine, C1-C2Alkyl substituted with 1-3 fluoro, methyl substituted with 1-3 chloro, methyl substituted with 1-3 bromo, ethyl substituted with 1-5 fluoro or ethyl substituted with 1-5 chloro.
Optionally, Y is selected from hydrogen, fluorine, chlorine, bromine, nitro, amino, cyano, C1-C2Alkyl or C substituted by chlorine, fluorine, nitro, amino, cyano1-C2Alkyl group of (1).
Alternatively, the R is1Selected from hydrogen, methyl, ethyl, amino, methyl substituted with 1-3 fluorines or methyl substituted with 1-3 chlorines; the R is2Selected from hydrogen, methyl, ethyl, amino, methyl substituted with 1-3 fluorines or methyl substituted with 1-3 chlorines; the R is3Selected from hydrogen, cyano, methyl or ethyl.
Alternatively, said X is selected from fluoro, chloro, bromo, nitro, amino, cyano, methyl substituted with 1-3 fluoro, methyl substituted with 1-3 chloro, ethyl substituted with 1-5 fluoro, or ethyl substituted with 1-5 chloro.
Preferably, in the phenyluracil compound shown in the formula I or the agriculturally pharmaceutically acceptable salt thereof, R is1Selected from hydrogen, amino, C1-C2Alkyl or C1-C2A haloalkyl group of (a);
the R is2Selected from hydrogen, amino, C1-C2Alkyl or C1-C2A haloalkyl group of (a);
the X and the Y are independently selected from hydrogen, halogen, nitro, amino, cyano and C1-C2Alkyl or C substituted by halogen, nitro, amino, cyano1-C2Alkyl groups of (a);
the R is3Selected from hydrogen, cyano or methyl;
the R is4Selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II;
in the substituent shown in the formula II, R is5Selected from halogens; the R is6The R is7Independently selected from halogen, C1-C4Alkyl or C1-C4A haloalkyl group of (a); the substituted phenyl group or the substituted aromatic heterocyclic group is substituted with one or two groups selected from: nitro, carboxyl, amino, methoxy, cyano, alkyl or haloalkyl.
Alternatively, the substituted phenyl or the substituted aromatic heterocyclic group contains 1 or 2 substituents.
Preferably, in the phenyluracil compound shown in the formula I or the agriculturally pharmaceutically acceptable salt thereof, R is1Selected from hydrogen, methyl, amino, trifluoromethyl;
the R is2Selected from hydrogen, methyl, amino, trifluoromethyl;
x is selected from hydrogen or halogen;
y is selected from hydrogen, halogen, nitro, amino, cyano or cyanomethyl;
the R is3Selected from hydrogen, methyl or cyano;
the R is4Selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II;
in the substituent shown in the formula II, R is5Selected from halogens; the R is6Selected from halogens; the R is7Selected from halogen, C1-C2Alkyl or C1-C2A haloalkyl group of (a); said substituted phenyl or said substituted aromatic heterocyclic group being substituted with one or two groups selected from: halogen, nitro, carboxyl, amino, methoxy, cyano, alkyl or haloalkyl.
Preferably, in the phenyluracil compound shown in the formula I or the agriculturally pharmaceutically acceptable salt thereof, R is1Selected from hydrogen, methyl, amino or trifluoromethyl;
the R is2Selected from hydrogen, methyl, amino or trifluoromethyl;
x is selected from hydrogen, fluorine, chlorine or bromine;
y is selected from hydrogen, fluorine, chlorine, bromine, nitro, amino, cyano or cyanomethyl;
the R is3Selected from hydrogen, cyano or methyl;
the R is4Is selected from substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II;
in the substituent shown in the formula II, R is5Selected from fluorine; the R is6Selected from fluorine; the R is7Selected from fluorine or C1-C2A haloalkyl group of (a); said substituted phenyl or said substituted aromatic heterocyclic group being substituted with one or two groups selected from: halogen, nitro, carboxyl, amino, methoxy, cyano, methyl or haloalkyl.
Preferably, in the phenyluracil compound shown in the formula I or the agriculturally and pharmaceutically acceptable salt thereof, R1Selected from hydrogen, methyl, amino or trifluoromethyl;
the R is2Selected from hydrogen, methyl, amino or trifluoromethyl;
x is selected from hydrogen, fluorine, chlorine or bromine;
y is selected from hydrogen, fluorine, chlorine, bromine, nitro, amino, cyano or cyanomethyl;
the R is3Selected from hydrogen, cyano or methyl;
the R is4Is selected from substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II;
in the substituent shown in the formula II, R is5Selected from fluorine; the R is6Selected from fluorine; the R is7Selected from fluorine or C1-C2A haloalkyl group of (a); the substituted phenyl group or the substituted aromatic heterocyclic group is substituted with one or two groups selected from: chlorine, nitro, methoxycarbonyl, cyano, methyl or trifluoromethyl, and the aromatic heterocyclic group includes pyrimidinyl, pyridyl, pyridazinyl, pyrazinyl, pyranyl, pyrazolyl, imidazolyl, thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl or isoxazolyl.
The aryl uracil compound or the agriculturally and pharmaceutically acceptable salt thereof in the first aspect of the invention has broad-spectrum weed-killing performance and has high-efficiency herbicidal activity for both grassy weeds and broad-leaved weeds; the aryl uracil compound or the agriculturally and pharmaceutically acceptable salt thereof also does not pose a hazard to mammals or the environment.
In a second aspect, the present invention also provides a method for preparing a phenyluracil compound or an agriculturally and pharmaceutically acceptable salt thereof, comprising the steps of:
providing or preparing a compound A as shown in a formula III, providing or preparing a compound B as shown in a formula IV,
wherein R is1、R2Independently selected from hydrogen, amino, C1-C4Alkyl or C1-C4A haloalkyl group of (a);
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-C4Alkyl or substituted C1-C4Alkyl groups of (a);
R3selected from hydrogen, cyano or C1-C4Alkyl groups of (a);
R4is selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II, wherein the aromatic heterocyclic group comprises aromatic five-membered heterocyclic group or aromatic six-membered heterocyclic group:
in the substituent group shown as the formula II, R5Selected from halogens; r6、R7Independently selected from hydrogen, halogen, C1-C4Alkyl or C1-C4A haloalkyl group of (a);
mixing the compound A and the compound B, then adding an acid-binding catalyst for reaction, collecting and purifying after the reaction is finished to obtain the phenyl uracil compound shown in the formula I,
optionally, the acid-binding catalyst may include, but is not limited to, triethylamine. The acid-binding catalyst can effectively catalyze and improve the reaction rate of the compound A and the compound B.
Optionally, after the reaction is finished, the process of collecting and purifying to obtain the phenyluracil compound shown in the formula i comprises: and carrying out acid washing, water washing and drying on the reacted solution, and then distilling and crystallizing to obtain the phenyl uracil compound. Wherein, the acid washing step can be carried out by adopting hydrochloric acid solution; and the water washing process comprises the step of washing the solution after the reaction by using deionized water until the solution is neutral, and then stopping the washing. Optionally, the drying process comprises drying with anhydrous sodium sulfate. Through the steps of acid washing and water washing, impurity components such as acid-binding catalysts and the like in the solution after the reaction can be effectively removed.
Optionally, performing a salt-forming reaction on the obtained phenyluracil compound, and then collecting and purifying to obtain an agriculturally acceptable salt of the phenyluracil compound. Optionally, the salifying reaction of the phenyluracil compound to obtain the phenyluracil compound includes: adding a proper alkali liquor or ammonia water into the phenyl uracil compound in an inert solvent, and purifying to obtain the agriculturally acceptable salt of the phenyl uracil compound I. Optionally, the inert agent comprises water; the alkali liquor comprises alkaline carbonate and hydroxide.
Alternatively, the compound a may be dissolved in any chemical agent capable of dissolving the compound a; the compound B is soluble in any chemical agent capable of dissolving the compound B. For example, the chemical agent may be, but is not limited to, one or more of dichloromethane, dichloroethane, and chloroform.
Optionally, part of the groups on the phenyluracil compound shown in formula I or the agriculturally and pharmaceutically acceptable salt thereof can also be substituted or replaced by, but not limited to, subsequent substitution reaction or other types of reaction. For example when R of said phenyluracils is3In the case of hydrogen, R can be recovered by chemical reaction3Phenyl uracils which are methyl or cyano.
The preparation method of the phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof provided by the second aspect of the invention is simple in process and can be used for industrial production, and the phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof prepared by the preparation method has good herbicidal activity, has high herbicidal activity for gramineae and broadleaf weeds, and can be widely used for agricultural production operation.
In a third aspect, the present invention provides a herbicidal composition comprising a phenyluracil compound according to the first aspect of the present invention or an agriculturally pharmaceutically acceptable salt thereof.
Optionally, the herbicide composition further comprises one or more of glyphosate, glufosinate, acetolactate synthase (ALS) inhibitors, acetyl-coa carboxylase (ACC) inhibitors, protoporphyrinogen oxidase (PPO) and p-hydroxyphenyl pyruvate dioxygenase (HPPD) inhibitors.
Optionally, the herbicidal composition further comprises other additives including one or more of liquid carriers, solid carriers, emulsifiers, surfactants, binders, thickeners, colorants, spreaders, antifreeze agents, anti-caking agents, disintegrants, and anti-decomposition agents. For example, the liquid carrier or the solid carrier, which is an inert substance, may be used to maintain the physical form of the phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof.
Optionally, the weight percentage of the phenyluracil compound or the agriculturally pharmaceutically acceptable salt thereof in the herbicide composition is 0.1-99.9%.
Alternatively, the herbicide composition may be applied by spraying, or by other means.
The herbicide composition of the third aspect of the invention is one of the applications of the phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof, and the herbicidal activity of the herbicide composition can be further improved through scientific proportioning; is beneficial to agricultural production and application. The targeting property, the weeding effect or the action time of the whole herbicide composition on weeds can be further improved by adjusting the active ingredients in the herbicide composition.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the raw materials and other chemicals used in the examples of the present invention are commercially available.
In this embodiment, the present invention provides a phenyluracil compound represented by formula i or an agriculturally and pharmaceutically acceptable salt thereof:
wherein R is1、R2Independently selected from hydrogen, amino, C1-C4Alkyl or C1-C4Alkyl halides of (2)A group;
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-C4Alkyl or substituted C1-C4Alkyl groups of (a);
R3selected from hydrogen, cyano or C1-C4Alkyl groups of (a);
R4is selected from cyano, nitro, substituted or unsubstituted phenyl, substituted or unsubstituted aromatic heterocyclic group or substituent shown as formula II, wherein the aromatic heterocyclic group comprises aromatic five-membered heterocyclic group or aromatic six-membered heterocyclic group:
in the substituent group shown as the formula II, R5Selected from halogens; r6、R7Independently selected from hydrogen, halogen, C1-C4Alkyl or C1-C4A haloalkyl group of (a).
Therefore, the phenyluracil compound shown in the formula I or the agriculturally pharmaceutically acceptable salt thereof includes various specific forms. For example, specific groups of a part of the aryluracil compounds or the agriculturally pharmaceutically acceptable salts thereof can be found in table 1, and all compounds in table 1 do not limit the group types of the aryluracil compounds or the agriculturally pharmaceutically acceptable salts thereof described herein.
Table 1: a list of groups of phenyluracils having the chemical structure shown in formula i or an agriculturally pharmaceutically acceptable salt thereof:
example 1 a method for producing a phenyluracil compound represented by compound number (1) in table 1:
the phenyl uracil compound shown in the compound number (1) is shown in a formula (1),
the preparation process comprises the following steps:
(1) preparation of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride, said 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride being a compound of formula a 1:
2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoic acid (V) (1.83g, 0.005mol) was added to 30mL of dichloromethane and stirred for half an hour; oxalyl chloride (1.90g, 0.015mol) was then slowly added dropwise, a few drops of N, N-Dimethylformamide (DMF) were then slowly added dropwise, and the mixture was heated under reflux at room temperature for 3 to 5 hours and spin-dried to give the desired product, 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (a1) (1.6g), in 84% yield. The 2-chloro-4-fluoro-5- (3-methyl) compoundNuclear magnetic resonance hydrogen spectrum characterization of-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (a 1):1H-NMR (400MHz in DMSO) data as follows, Δ 8.544(d, J. 7.6Hz,1H, Ar), 8.072(d, J. 9.6Hz,1H, Ar), 6.876(s,1H, CH), 3.984(s,3H, -CH3). 2-chloro-4-fluoro-5- (1,2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethylpyrimidin-1-yl) benzoyl chloride (1.59g,0.0041mol) was dissolved in 20mL of dichloromethane to prepare A1 solution.
(2) Preparing trifluoromethanesulfonamide, wherein the trifluoromethanesulfonamide is a compound shown as a chemical formula (B1):
adding trifluoromethanesulfonyl chloride (0.72g, 0.0043mol) into 15mL of tetrahydrofuran, stirring for half an hour by using a magnetic stirrer, then slowly dropwise adding 5mL of ammonia water, and reacting for 3h at normal temperature; after completion of the reaction, the resulting material was spun dry to give trifluoromethanesulfonamide (B1) (0.61g, 0.0041mol, 96% yield) as a white solid. The trifluoromethanesulfonamide (0.61g, 0.0041mol, 96% yield) was dissolved in 20mL of dichloromethane to prepare a B1 solution.
(3) Slowly dripping the solution A1 into the solution B1 at the temperature of 0-5 ℃, then adding 0.436g of triethylamine, and reacting at room temperature for 2-3h after dripping is finished; after the reaction, the reaction product was washed with 2M hydrochloric acid for 2 to 3 times and then with water for 2 to 3 times to wash off excess triethylamine, wherein the organic phase of the reacted solution was washed with water to neutrality, and then dried with anhydrous sodium sulfate, and finally dried by spin-drying to obtain 1.83g of a phenyluracil compound represented by compound number (1) as a white powder, with a yield of 90%.
Hydrogen nuclear magnetic resonance spectroscopy:1H-NMR (400MHz, DMSO), data as follows: δ 8.044(d, J ═ 8Hz,1H, Ar), 7.833(d, J ═ 9.6Hz,1H, Ar), 6.606(s,1H, CH), 3.403(s,3H, -CH)3)。
In this example, there is also provided a process for preparing 2-chloro-4-fluoro-5- (1,2,3, 6-tetrahydro-2, 6-dioxo-3-methyl-4-trifluoromethylpyrimidin-1-yl) benzoic acid (v), according to the reaction scheme shown in formula (C1), comprising:
(a) preparation of 2-chloro-4-fluoro-5-aminobenzoic acid:
heating and refluxing a 20mL solution of 2-chloro-4-fluoro-5-nitrobenzoic acid (1 g; 0.0046mol) in acetic acid; fe powder (1.02g, 0.0182mol) was added in portions, the suspension was cooled to room temperature, diluted with water and ethyl acetate, filtered and the filtrate was collected. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give 2-chloro-4-fluoro-5-aminobenzoic acid as a brown solid in a yield of 0.55g of 63.9%.
(b) Preparation of 2-chloro-5- (2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) -4-fluorobenzoic acid:
a mixture of 2-chloro-4-fluoro-5-aminobenzoic acid (0.69g, 0.0036mol), 2-dimethylamino-4 (trifluoromethyl) -6H-1, 3-oxazin-6-one (0.80g, 0.0038mol) and acetic acid was stirred under reflux for 2-3H, diluted with ice water and then extracted 2 times with ethyl acetate; then, the organic layers were combined, washed with brine, dried over anhydrous magnesium sulfate, filtered under suction, and concentrated under reduced pressure to give 1.12g of 2-chloro-5- (2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) -4-fluorobenzoic acid in 88.2% yield.
(c) Preparation of methyl 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoate:
a mixture of 2-chloro-5- (2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) -4-fluorobenzoic acid (1.48g, 0.0042mol), potassium carbonate (1.44g, 0.010mol), iodomethane (0.650mL, 0.010mol) and dimethylformamide (16.67mL) was stirred at room temperature for 8H, then diluted with water (60 mL); extracting twice with ethyl acetate; the organic layers were combined, the combined organic layers were washed three times with water, aqueous sodium hydroxide (1M) and brine, the organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a beige solid; finally, recrystallization from ethanol-water (30mL) gave 1.1g of methyl 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoate in 68.8% yield. Nuclear magnetic resonance hydrogen spectrometerCharacterized by the following:1H-NMR(300MHz CDCl3) The data are as follows, δ 7.92(d, J ═ 7.8Hz,1H, Ar), 7.40(d, J ═ 9.0Hz,1H, Ar), 6.38(s,1H, CH), 3.91(s,1H, CH)3)，3.57(s,3H,NCHNCH3)。
(d) 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoic acid preparation:
methyl 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoate (1.37g, 3.67mmol) was dissolved in 15mL of glacial acetic acid under heating, 15mL of concentrated hydrochloric acid was added, the temperature was raised to 85 ℃ to react for 8H, the reaction solution was cooled to room temperature, the reaction solution was poured into a beaker containing 40mL of water, and a white solid was precipitated under stirring, followed by suction filtration and drying to obtain 1.25g of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoic acid with a yield of 93.5%.
In the above-mentioned preparation method, when the substituent chlorine in 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoic acid is replaced by cyano or other substituent, it can be prepared by the same method; other compounds having a structure similar to that of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoic acid can also be prepared by the corresponding adjustment process of the above preparation method, and will not be described in detail in this embodiment.
Example 2 a method for producing a phenyluracil compound represented by compound number (27) in table 1:
the phenyl uracil compound shown in the compound number (27) is shown as a formula (2),
the preparation process comprises the following steps:
(1) preparation of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (a 2):
2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (A2) (1.59g,0.0041mol) was dissolved in 20mL of dichloromethane to prepare A2 solution.
(2) Preparation of 3-chloro-benzenesulfonamide (B2)
Adding 3-chloro-benzenesulfonyl chloride (0.9g, 0.0043mol) into 15mL of tetrahydrofuran, stirring for half an hour by using a magnetic stirrer, then slowly dropwise adding 5mL of ammonia water, and reacting for 3 hours at normal temperature; after completion of the reaction, 3-chloro-benzenesulfonamide (B2) (0.78g, 0.0041mol, 95% yield) was obtained as a white solid by spin-drying. The 3-chloro-benzenesulfonamide (0.78g, 0.0041mol) thus prepared was dissolved in 20mL of dichloromethane to prepare a B2 solution.
(3) Slowly dripping the solution A2 into the solution B2 at the temperature of 0-5 ℃, then adding 0.435g of triethylamine, and reacting at room temperature for 2-3h after dripping is finished; and after the reaction is finished, washing the reaction product with 2M hydrochloric acid for 2 to 3 times, then washing the reaction product with water for 2 to 3 times, and washing off redundant triethylamine, wherein an organic phase of the solution after the reaction is washed to be neutral by water, then adding anhydrous sodium sulfate for drying, and performing spin drying to obtain 1.99g of the phenyluracil compound shown in the compound number (27) in a white powder form, wherein the yield is 90%.
Hydrogen nuclear magnetic resonance spectroscopy:1H-NMR (400MHz, DMSO) data as follows, δ 8.398(s,1H, Ar), 8.158(d, J ═ 7.6Hz,1H, Ar), 8.082(d, J ═ 8.0Hz,1H, Ar), 8.037(d, J ═ 8.0Hz,1H, Ar), 7.833(d, J ═ 9.6Hz,1H, Ar), 7.746(m,1H, Ar), 7.531(s,1H, NH), 6.601(s,1H, CH), 3.909(s,3H, -CH, CH), 3.909(s,3H, -H, Ar, and r), and3)。
example 3 a method for producing a phenyluracil compound represented by compound number (37) in table 1:
the phenyl uracil compound shown in the compound number (37) is shown as a formula (3),
the preparation process comprises the following steps:
(1) preparation of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (a 3):
dissolving 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (0.335g) in dichloromethane to prepare A3 solution;
(2) preparation of methyl 3- (aminosulfonyl) benzoate (B3):
wherein, the preparation process of the methyl 3- (aminosulfonyl) benzoate (B3) is shown in a reaction formula (C2) and comprises the following steps:
3- (chlorosulfonyl) benzoic acid (3.97g) was added to a single-neck flask equipped with a magnetic stirrer, a small amount of dichloromethane was added, 6.9g of oxalyl chloride was added, 5 drops of N, N-Dimethylformamide (DMF) were added, and then the mixture was heated under reflux and kept warm for 2 hours, after the reaction was completed, the solvent was distilled off under reduced pressure to obtain 3- (chlorosulfonyl) benzoyl chloride as a yellow oily liquid to be used directly in the next reaction. Then adding tetrahydrofuran into 3- (chlorosulfonyl) benzoyl chloride for dissolving, adding 1.5mL of methanol, reacting at room temperature for 10 hours, evaporating the solvent in a rotary manner to obtain yellow oily liquid, and recrystallizing with petroleum ether to obtain 2.45g of 3- (chlorosulfonyl) methyl benzoate white solid; the overall two-step yield was 58.3%.
Dissolving methyl 3- (chlorosulfonyl) benzoate (1g, 4.26mmol) in tetrahydrofuran (15mL), cooling the solution to 0 ℃, then slowly adding dropwise (5mL) ammonia water, stirring at room temperature after dropwise addition, and reacting for 2 hours; after completion of the reaction, the reaction mixture was poured into cold water and extracted with ethyl acetate; then washing the extracted ethyl acetate solution with NaCl solution, drying with anhydrous sodium sulfate after washing, filtering, and spin-drying ethyl acetate under reduced pressure to obtain a white product, namely 0.65g of methyl 3- (aminosulfonyl) benzoate, wherein the yield is 71%; methyl 3- (aminosulfonyl) benzoate (0.178g) was dissolved in 20mL of methylene chloride to prepare a solution B3;
(3) slowly dripping the A3 solution into the B3 solution at the temperature of 0-5 ℃, controlling the temperature to be low, then slowly adding 0.0871g of triethylamine as an acid-binding catalyst, slowly heating to room temperature after dripping is finished, reacting for 2-3h, transferring into a separating funnel, washing twice with 2M hydrochloric acid, washing an organic phase to be neutral with water, adding anhydrous sodium sulfate for drying, performing suction filtration, and performing rotary drying and concentration to obtain 0.421g of the phenyluracil compound shown by the compound number (27) in a viscous solid state, wherein the yield is 82.1%.
Nuclear magnetic resonance hydrogen spectrum (1H-NMR, DMSO, 400MHz) data as follows, δ: 8.937(s,1H, Ar), 8.647(d, J-8.80 Hz,1H, Ar), 8.578(d, J-8.00, 1H, Ar), 8.238(d, J-8.40, 1H, Ar), 8.169(m,1H, Ar), 7.818(d, J-9.60, 1H, Ar), 7.233(s,1H, NH),6.841(s,1H, CH), 4.380(s,3H, -OCH)3)，3.971(s,3H,-NCH3)。
Example 4 a method for producing a phenyluracil compound represented by compound number (175) in table 1:
the phenyl uracil compound shown in the compound number (175) is shown as a formula (4),
(1) preparation of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (a 4):
dissolving 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (0.44g) in dichloromethane (10mL) to prepare A4 solution;
(2) preparing 3, 5-dimethyl-isoxazole-4-sulfonamide (B4), said 3, 5-dimethyl-isoxazole-4-sulfonamide:
in a three-necked flask, 3, 5-dimethyl-isoxazole-4-sulfonamide (0.21g) was dissolved in dichloromethane (10mL) to prepare a B4 solution;
(3) and (3) dropwise adding 5 drops of triethylamine mixture into the B4 solution at the low temperature of 0-10 ℃, slowly dropwise adding the A4 solution into the B4 solution, controlling the low temperature, returning to room temperature to react for 4 hours after the dropwise adding is finished, and finishing the reaction. Washed twice with 2M hydrochloric acid, several layers washed with distilled water to neutrality, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain the target product, 2-chloro-N- (3, 5-dimethyl-isoxazol-4-ylsulfonyl) -4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzamide, in light yellow solid 0.50g with 82.0% yield.
Nuclear magnetic resonance hydrogen spectrum (1H-NMR,DMSO,400MHz)8.021(d,J＝8.4Hz,1H,Ar)，7.816(d,J＝10.0Hz,1H,Ar)，7.583(s,1H,NH)，6.586(s,1H,CH)，3.397(s,3H,-NCH3)，2.546(s,3H,-CH3)，2.329(s,3H,-NCH3)
The phenyl uracil compounds shown by the numbers of other compounds in table 1 can be prepared by corresponding adjustment in the preparation methods described in the above examples; this embodiment will not be described in detail.
Effect example 1
The test for determining the herbicidal activity of the phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof comprises the following steps:
in order to effectively prove the beneficial effects of the novel phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof provided by the invention, a part of the phenyluracil compound shown in table 1 is selected to carry out a determination experiment of the herbicidal activity, and the experimental approximate steps comprise:
determining the herbicidal activity of the target compound by adopting a post-emergence stem and leaf treatment experimental method;
(1) collecting soil without pesticide, sowing, germinating, spraying stem and leaf until the gemini leaves grow to 2-4 leaves and the monozygotic leaves grow to 3-4 leaves, dissolving the compound with a small amount of organic solvent, adding a small amount of emulsifier, diluting with water to obtain solution containing the compound, and preparing saflufenacil as a control group as shown in formula (5),
(2) the plant naturally grows under the laboratory condition, and the potted plant is replenished with water every day; the survey results after 15 days are shown in table 3, wherein the herbicide scoring criteria are shown in table 2; in this experiment, the test target was selected from the following common gramineae weeds: barnyard grass, large crabgrass, goosegrass, and broadleaf weeds: amaranth and purslane.
Table 2: herbicide rating criteria
Table 3: table 1 comparison table of herbicide scores for herbicidal activity inhibition (%) of some phenyluracils and saflufenacil
Note: the compound numbers correspond to those in Table 1
The result shows that the phenyl uracil compound provided by the invention has higher herbicidal activity on gramineae and broadleaf weeds; the prior saflufenacil has weeding activity on broadleaf weeds and has poor effect on grassy weeds; therefore, the phenyl uracil compound provided by the invention has a wide weed removal range and has high-efficiency herbicidal activity.
It is noted that the phenyluracil compounds shown in compound numbers (1), (2) and (7) provided by the invention have more outstanding herbicidal activity on weeds such as goosegrass which is difficult to control; and the phenyl uracil compounds shown by other selected compound numbers also show higher herbicidal activity on weeds such as goosegrass herb and the like.
Effect example 2
And (3) sowing a certain amount of rice seeds in a flowerpot of the soil without medicine, watering thoroughly, carrying out stem and leaf spraying treatment on 4 leaves of the rice, and investigating the result after 15 days. It was found by the safety measurement that the phenyluracils of the present embodiment, which are represented by the compound numbers (1), (26), (27), (28), (29), (36), (37), (38), (138), (139), (151), (152) and (175), are highly safe for rice at a dose of 8 to 32 g/ha. The phenyl uracil compound of the present invention can protect crop and has wide weed eliminating range and high herbicidal activity.
Effect example 3
A comparison experiment of the herbicidal activity inhibition (%) of the phenyluracil compound or the agriculturally and pharmaceutically acceptable salt thereof and glyphosate is as follows:
the phenyl uracil compounds (represented by the compound (1)) shown in the compound number (1) are selected to have comparative herbicidal effects with the herbicide glyphosate disclosed in the prior art, and see table 4.
Table 4: comparison table of herbicidal activity inhibition (%) of phenyluracil compounds represented by Compound No. 1 with Glyphosate compositions
The result shows that the phenyluracil compound shown in the compound number (1) provided by the invention has more outstanding herbicidal activity compared with glyphosate; meanwhile, when the composition of the phenyluracil compound shown in the compound number (1) and the glyphosate shows more effective herbicidal activity, the composition shows more excellent herbicidal effect than the phenyluracil compound shown in the compound number (1) or the glyphosate used alone; the phenyluracil compound shown in the compound number (1) and the glyphosate have good synergistic weeding effect, and can be used for preventing and removing the eleusine indica which is difficult to control.
In this embodiment, when the glyphosate is replaced with other herbicide components, the resulting herbicide composition also has good herbicidal activity.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (8)
1. A phenyluracil compound represented by formula I or an agriculturally pharmaceutically acceptable salt thereof:
wherein R is1、R2Independently selected from hydrogen, amino, C1-C4Alkyl or C1-C4A haloalkyl group of (a);
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-C4Alkyl or C substituted by chlorine, fluorine, nitro, amino, cyano1-C2Alkyl groups of (a);
R3selected from hydrogen, cyano or C1-C4Alkyl groups of (a);
R4selected from substituted or unsubstituted phenyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl; the substituted phenyl, the substituted oxazolyl, the substituted isoxazolyl are each substituted with one or two groups selected from: halogen, nitro, C1-C4Alkoxycarbonyl or cyano of (a).
2. A phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof according to claim 1, wherein the substituted phenyl, the substituted oxazolyl or the substituted isoxazolyl are each substituted by one or two groups selected from: chloro, nitro, methoxycarbonyl or cyano.
3. A phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof according to claim 1, wherein Y is selected from hydrogen, fluoro, chloro, bromo, nitro, amino, cyano, C1-C2Alkyl or C substituted by chlorine, fluorine, nitro, amino, cyano1-C2Alkyl group of (1).
4. The phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof according to claim 1, wherein R is1Selected from hydrogen and AAlkyl, ethyl, amino, methyl substituted with 1-3 fluorines or methyl substituted with 1-3 chlorines; the R is2Selected from hydrogen, methyl, ethyl, amino, methyl substituted with 1-3 fluorines or methyl substituted with 1-3 chlorines; the R is3Selected from hydrogen, cyano, methyl or ethyl.
5. A phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof according to claim 1, wherein X is selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, methyl substituted by 1-3 fluorine, methyl substituted by 1-3 chlorine, ethyl substituted by 1-5 fluorine and ethyl substituted by 1-5 chlorine.
6. A preparation method of a phenyluracil compound or an agriculturally and pharmaceutically acceptable salt thereof is characterized by comprising the following steps:
providing or preparing a compound A as shown in a formula III, providing or preparing a compound B as shown in a formula IV,
wherein R is1、R2Independently selected from hydrogen, amino, C1-C4Alkyl or C1-C4A haloalkyl group of (a);
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-C4Alkyl or C substituted by chlorine, fluorine, nitro, amino, cyano1-C2Alkyl groups of (a);
R3selected from hydrogen, cyano or C1-C4Alkyl groups of (a);
R4selected from substituted or unsubstituted phenyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted isoxazolyl; the substituted phenyl, the substituted oxazolyl, the substituted isoxazolyl are each substituted with one or two groups selected from: halogen, nitro, C1-C4Alkoxycarbonyl of (a)A group or a cyano group;
mixing the compound A and the compound B, then adding an acid-binding catalyst for reaction, collecting and purifying after the reaction is finished to obtain the phenyl uracil compound shown in the formula I,
7. a herbicidal composition comprising the phenyluracil compound or an agriculturally pharmaceutically acceptable salt thereof according to any one of claims 1 to 5.
8. The herbicidal composition of claim 7, further comprising one or more of glyphosate, glufosinate, acetolactate synthase inhibitors, acetyl-coa carboxylase inhibitors, protoporphyrinogen oxidase, and p-hydroxyphenyl pyruvate dioxygenase inhibitors.
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| WO1996016043A1 (en) * | 1994-11-17 | 1996-05-30 | Bayer Aktiengesellschaft | Substituted diazacyclohexane di(thi)ons having a herbicidal effect |
| CN1383425A (en) * | 2000-05-04 | 2002-12-04 | 巴斯福股份公司 | Uracil substituted phenyl sulfamoyl carboxamides |
| CN1758851A (en) * | 2003-03-13 | 2006-04-12 | 巴斯福股份公司 | Herbicidal mixtures based on 3-phenyluracils |
| CN105682465A (en) * | 2013-09-18 | 2016-06-15 | 瑞戴格作物保护公司 | Agricultural chemicals |
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| WO1996016043A1 (en) * | 1994-11-17 | 1996-05-30 | Bayer Aktiengesellschaft | Substituted diazacyclohexane di(thi)ons having a herbicidal effect |
| CN1383425A (en) * | 2000-05-04 | 2002-12-04 | 巴斯福股份公司 | Uracil substituted phenyl sulfamoyl carboxamides |
| CN1758851A (en) * | 2003-03-13 | 2006-04-12 | 巴斯福股份公司 | Herbicidal mixtures based on 3-phenyluracils |
| CN105682465A (en) * | 2013-09-18 | 2016-06-15 | 瑞戴格作物保护公司 | Agricultural chemicals |
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