CN117534624A - Uracil benzene ring ester compound, preparation method thereof and pesticide composition - Google Patents

Uracil benzene ring ester compound, preparation method thereof and pesticide composition Download PDF

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CN117534624A
CN117534624A CN202311390249.3A CN202311390249A CN117534624A CN 117534624 A CN117534624 A CN 117534624A CN 202311390249 A CN202311390249 A CN 202311390249A CN 117534624 A CN117534624 A CN 117534624A
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alkoxycarbonyl
uracil
substituted
ester compound
alkyl
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王明良
莫方婷
左佳祺
袁程
王利菲
朱才镇
徐坚
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Shenzhen University
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Shenzhen University
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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
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The application provides uracil benzene ring ester compounds shown as a formula (I), wherein R 1 、R 2 Independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl; x, Y is independently selected from hydrogen, halogen or cyano; z is selected from oxygen atom or sulfur atom; r3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl, or C2-C8 alkynyl substituted by C1-C8 alkoxycarbonyl. The uracil benzonitrile ester compound has high selectivity and wide weeding spectrum, and has good effect of preventing and killing broadleaf weeds such as amaranth, grassy weeds such as barnyard grass, and the like. The invention also provides a preparation method of the uracil benzene ring ester compound and a pesticide composition.

Description

Uracil benzene ring ester compound, preparation method thereof and pesticide composition
Technical Field
The invention relates to the technical field of organic compounds, in particular to a uracil benzene ring ester compound, a preparation method thereof and a pesticide composition.
Background
The current main method of weed control is by spraying herbicides. However, with the widespread use of herbicides (e.g., glyphosate), a large number of weeds have developed resistance, and particularly weeds such as barnyard grass, moleplant, goosegrass, and the like have developed into a dominant weed and a malignant weed. The existing market has the characteristics of poor control effect, narrow weed removal range, high dosage medication and the like of various herbicides, and has poor killing effect on malignant weeds such as barnyard grass, semen euphorbiae and the like. Meanwhile, the selective herbicide often has adverse effects on the growth of crops, and particularly has huge economic losses on vegetables such as cabbages and the like.
Therefore, it is necessary to provide a novel herbicidal compound which has a high selectivity, a broad herbicidal spectrum, is less likely to cause resistance to weeds, has a good herbicidal effect against malignant weeds such as barnyard grass, and is safe against cabbages.
Disclosure of Invention
In view of the above, the application provides a uracil benzene ring ester compound, which has the advantages of high selectivity, wide weeding spectrum, difficult generation of resistance to weeds, good prevention and removal effect on barnyard grass, semen euphorbiae, amaranth and other malignant weeds, low toxicity to mammals, small influence on crops and the like.
The first aspect of the application provides an uracil benzene ring ester compound shown as a formula (I):
in the formula (I), R 1 、R 2 Each independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl or C1-C8 alkynyl substituted by C1-C8 alkoxycarbonyl.
In the embodiment of the application, R is 3 Is C1-C4 alkoxycarbonyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkoxy, C1-C4 alkoxycarbonyl-substituted C2-C8 alkenyl or C1-C4 alkoxycarbonyl-substituted C2-C8 alkynyl.
In the embodiment of the application, R is 3 Is C1-C4 alkoxycarbonyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkoxy, C1-C4 alkoxycarbonyl-substituted C2-C8 alkenyl or C1-C4 alkoxycarbonyl-substituted C2-C8 alkynyl.
In the embodiment of the application, R is 3 Is C1-C2 alkoxycarbonyl, C1-C2 alkoxycarbonyl-substituted C1-C4 alkyl, C1-C2 alkoxycarbonyl-substituted C1-C2 alkoxy, C1-C2 alkoxycarbonyl-substituted C2-C4 alkenyl or C1-C2 alkoxycarbonyl-substituted C2-C4 alkynyl.
In the embodiment of the application, R is 1 Is a C1-C4 perfluoroalkyl group; the R is 2 Is C1-C4 alkyl; the X, Y is halogen.
In the embodiment of the application, R is 1 Is trifluoromethyl; the R is 2 Methyl or ethyl; the X, Y groups are each independently selected from fluorine or chlorine.
The second aspect of the application also provides a preparation method of uracil benzene ring ester compounds, which comprises the following steps:
providing a compound A shown as a formula (II) and a compound B shown as a formula (III),
wherein R is 1 、R 2 Independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloAlkyl substituted;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl or C2-C8 alkynyl substituted by C1-C8 alkoxycarbonyl;
mixing the compound A and the compound B, adding a catalyst for reaction, collecting a solid product after the reaction is finished, purifying to obtain uracil benzene ring ester compounds shown as a formula (I),
in embodiments of the present application, the reaction temperature of the reaction is from 0 ℃ to 160 ℃.
In the embodiment of the application, the reaction time of the reaction is 2-15 h.
A third aspect provides a pesticidal composition comprising an active ingredient comprising a uracil phenyl ester compound provided in the first aspect of the present application or an agropharmaceutically acceptable salt thereof or a uracil phenyl ester compound prepared by a method of preparing a uracil phenyl ester compound provided in the second aspect of the present application or an agropharmaceutically acceptable salt thereof; the mass percentage of the active components in the pesticide composition is 1-99%.
The fourth aspect of the application also provides an application of the uracil benzene ring ester compound provided in the first aspect of the application or the pesticide composition provided in the third aspect in herbicide or defoliant.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Because of the competition with crops for light and fertilizer water, weeds cause great loss to crop production each year, and the main method for preventing and controlling weeds is to spray herbicides at present. However, with the widespread use of herbicides (e.g., glyphosate), a large number of weeds have developed resistance, and particularly weeds such as barnyard grass, moleplant, goosegrass, and the like have developed into a dominant weed and a malignant weed. The existing market has the characteristics of poor control effect, narrow weed removal range, high dosage medication and the like of various herbicides, and has poor killing effect on malignant weeds such as barnyard grass, semen euphorbiae and the like. Meanwhile, the selective herbicide often has adverse effects on the growth of crops, and particularly has huge economic losses on vegetables such as cabbages and the like.
Therefore, it is necessary to provide a novel herbicidal compound which has a high selectivity, a broad herbicidal spectrum, is less likely to cause resistance to weeds, has a good herbicidal effect against malignant weeds such as barnyard grass, and is safe against cabbages.
In view of the above, the application provides a uracil benzene ring ester compound, which has the advantages of high selectivity, wide weeding spectrum, difficult generation of resistance to weeds, good prevention and removal effect on barnyard grass, semen euphorbiae, amaranth and other malignant weeds, low toxicity to mammals, small influence on crops and the like.
The application provides uracil benzene ring ester compounds shown as a formula (I):
in the formula (I), R 1 、R 2 Each independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkoxycarbonyl-substituted C1-C8 alkyl, C1-C8 alkoxycarbonyl-substituted C1-C8 alkoxy, C1-C8 alkoxycarbonyl-substituted C2-C8 alkenyl or C1-C8 alkoxycarbonyl-substituted C2-C8 alkynyl.
In embodiments of the present application, R 1 、R 2 Each independently selected from C1-C4 alkyl or C1-C4 haloalkyl. In some embodiments of the present application, C1-C4 alkyl may be, for example, methyl, ethyl, propyl, isopropyl, or butyl; the C1-C4 haloalkyl group may be, for example, methyl, ethyl, propyl, isopropyl or butyl substituted with at least one halogen atom. In embodiments of the present application, the halogen atom in the C1-C4 haloalkyl group may be a fluorine atom, a chlorine atom, a bromine atom. In embodiments of the present application, the halogen atom of the C1-C4 haloalkyl group may be one or more.
In some embodiments of the present application, R 1 、R 2 Each independently is C1-C2 alkyl or C1-C2 haloalkyl. In some embodiments of the present application, R 1 、R 2 Examples are methyl, ethyl, monochloromethyl, dichloromethyl, trichloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, R 1 、R 2 May be the same group or different groups. In some embodiments of the present application, R 1 For example, trifluoromethyl; r is R 2 For example, methyl.
In embodiments of the present application, R 3 Can be at any position of benzene ring where R is 3 May be ortho, meta or para to Z.
In this embodiment, the C1-C8 alkoxycarbonyl group includes a linear alkoxycarbonyl group having 1 to 8 carbon atoms, a branched alkoxycarbonyl group having 1 to 8 carbon atoms and a cyclic alkoxycarbonyl group having 3 to 8 carbon atoms. In some embodiments of the present application, the number of carbon atoms of the C1-C8 alkoxycarbonyl group may be, for example, 1,2,3, 4, 5, 6, 7, 8. In some embodiments of the present application, the C1-C8 alkoxycarbonyl group may be, for example, -COOCH 3 、-COOCH 2 CH 3 、-COOCH 2 CH 2 CH 3 、-COOCH(CH 3 ) 2 、-COOCH(CH 3 )CH 2 CH 3 、-COOC(CH 3 ) 3 、-COOCH(CH 2 CH 2 )、-COOC(CH 2 CH 2 )CH 3 。
In the present embodiment, the C1-C8 alkyl group includes a straight-chain alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. In some embodiments of the present application, the number of carbon atoms of the C1-C8 alkyl group may be, for example, 1,2,3, 4, 5, 6, 7, 8. In the present embodiment, the C1-C8 alkoxy group includes a straight chain alkoxy group having 1 to 8 carbon atoms, a branched chain alkoxy group having 1 to 8 carbon atoms, and a cycloalkoxy group having 3 to 8 carbon atoms. In some embodiments of the present application, the number of carbon atoms of the C1-C8 alkoxy group may be, for example, 1,2,3, 4, 5, 6, 7, 8.
In embodiments of the present application, C2-C8 alkenyl includes straight chain alkenyl groups having 2 to 8 carbon atoms and branched alkenyl groups having 2 to 8 carbon atoms. In some embodiments of the present application, the number of carbon atoms of the C2-C8 alkenyl group may be, for example, 2,3, 4, 5, 6, 7, 8. In this embodiment, the C2-C8 alkynyl group includes a straight-chain alkynyl group having 2 to 8 carbon atoms and a branched-chain alkynyl group having 2 to 8 carbon atoms. In some embodiments of the present application, the number of carbon atoms of the C2-C8 alkynyl group can be, for example, 2,3, 4, 5, 6, 7, 8.
In some embodiments of the present application, R 3 Is C1-C4 alkoxycarbonyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkoxy, C1-C4 alkoxycarbonyl-substituted C2-C8 alkenyl or C1-C4 alkoxycarbonyl-substituted C2-C8 alkynyl.
In some embodiments of the present application, R 3 Is C1-C2 alkoxycarbonyl, C1-C2 alkoxycarbonyl-substituted C1-C4 alkyl, C1-C2 alkoxycarbonyl-substituted C1-C2 alkoxy, C1-C2 alkoxycarbonyl-substituted C2-C4 alkenyl or C1-C2 alkoxycarbonyl-substituted C2-C4 alkynyl.
In some embodiments of the present application, the R 1 Is a C1-C4 perfluoroalkyl group; the R is 2 Is C1-C4 alkyl; the X, Y is halogen.
In some embodiments of the present application, the R 1 Is trifluoromethyl; the R is 2 Methyl or ethyl; the X, Y groups are each independently selected from fluorine or chlorine.
Compared with the traditional herbicide compound, the uracil-benzofuranyl ester compound provided by the application has stronger weeding effect and more outstanding selectivity. The uracil benzene ring ester compound provided by the application can improve the selectivity of the compound through the selection of corresponding groups, and enlarge the weeding type range, and the original plants or crops are not influenced as much as possible while malignant weeds are effectively removed. The selection of each group in the structure of the phencyclized ester compound can greatly improve the selectivity and the weeding spectrum range, so that the phencyclized ester compound has the advantages of high selectivity, wide weeding spectrum, difficult generation of resistance to weeds, good prevention and removal effect on malignant weeds such as barnyard grass, low toxicity to mammals, small influence on crops and the like.
The application also provides a preparation method of the uracil benzene ring ester compound, which comprises the following steps:
s101, providing a compound A shown as a formula (II) and a compound B shown as a formula (III),
wherein R is 1 、R 2 Each independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl or C2-C8 alkynyl substituted by C1-C8 alkoxycarbonyl;
s102, mixing the compound A with the compound B, adding a catalyst for reaction, collecting a solid product after the reaction is finished, purifying to obtain the uracil benzene ring ester compound shown in the formula (I),
in the present embodiment, the catalyst in step S102 includes, but is not limited to, an acid-binding catalyst.
In the present embodiment, the reaction temperature of the reaction in step S102 is 0 ℃ to 160 ℃. In some embodiments of the present application, the reaction temperature of the reaction in step S102 may be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 50 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 160 ℃.
In the embodiment of the present application, the reaction time of the reaction in step S102 is 2h to 15h. In some embodiments of the present application, the reaction time of the reaction in step S102 may be, for example, 2h, 3h, 5h, 8h, 10h, 12h, 15h.
The preparation method of uracil benzene ring ester compounds provided by the application is simple and convenient, less in pollution and high in yield, and the preparation method can be suitable for industrial production. The uracil benzene ring ester compound prepared by the preparation method has the advantages of high selectivity, low dosage, wide weeding spectrum, difficult generation of resistance of weeds, good prevention and removal effect on malignant weeds such as barnyard grass, low toxicity to mammals, small influence on crops and the like.
The application also provides a pesticide composition, which comprises an active component, wherein the active component comprises uracil phenyl ring ester compounds provided by the application or pharmaceutically acceptable salts thereof or uracil phenyl ring ester compounds prepared by the preparation method of the uracil phenyl ring ester compounds provided by the application or pharmaceutically acceptable salts thereof; the mass percentage of the active components in the pesticide composition is 1-99%. In some embodiments of the present application, the mass percent of active component in the pesticide composition may be, for example, 1%, 2%, 5%, 8%, 5%, 10%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 99%. In embodiments of the present application, the pesticide composition may be used by means including, but not limited to, spraying.
The application also provides application of the uracil benzene ring ester compound provided by the application or the pesticide composition provided by the application in herbicide or defoliant. In some embodiments of the present application, the uracil-benzonitrile ester compound is used for herbicide, and the mass percentage of the uracil-benzonitrile ester compound in the herbicide is 0.1% -99.9%. In some embodiments of the present application, the mass percentage of uracil benzonitrile ester compound in the herbicide may be, for example, 0.1%, 0.5%, 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 70%, 80%, 90%, 99.9%. In some embodiments of the present application, the uracil phenyl ester compound may be present in the herbicide in an amount of 0.1% -40% by mass. The uracil benzonitrile ester compound provided by the application is applied to herbicide, so that the herbicide which has high selectivity, low dosage, wide weeding spectrum and less possibility of generating resistance to weeds, and especially has better preventing and killing effect on malignant weeds such as barnyard grass and the like can be obtained.
In other embodiments of the present application, the uracil benzene ring ester compound is used in a defoliating agent, and the mass percentage of the uracil benzene ring ester compound in the defoliating agent is 0.1% -99.9%. In some embodiments of the present application, the mass percentage of uracil benzonitrile ester compounds in the herbicide may be, for example, 0.1%, 1%, 5%, 10%, 15%, 20%, 23%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 60%, 70%, 80%, 90%, 99.9%. In some embodiments of the present application, the uracil phenyl ester compound may be 20% -50% by mass of the herbicide. The uracil benzene ring ester compound provided by the application is applied to defoliating agents, can be suitable for defoliating requirements of various plants, and for example, the defoliating agents are used for defoliating cotton crops and show obvious defoliating effects.
The embodiments of the present application are further described below in terms of a number of examples.
Specifically, the uracil benzonitrile ester compounds described in the section of this application are shown in table 1, but the benzonitrile ester compounds described in the present invention are not limited to all compounds in table 1.
Note that: r is R 3 The ortho position of the benzene ring is marked as the 1 st position, R 3 The meta position of the benzene ring is 2, R 3 The para position of the benzene ring is the 3-position.
Table 1: uracil benzene ring ester compound with chemical structural formula as shown in formula (I):
example 1
The preparation method of uracil benzene ring ester compound shown in compound number 1 in table 1 comprises the following steps:
(1) 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoic acid (1.0 g,0.0026 mol) was added to thionyl chloride, heated at room temperature under reflux for 6h, and dried by spinning to give the desired product 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoyl chloride (0.8387 g,0.0022 mol) in 84% yield. The nuclear magnetic resonance hydrogen spectrum of the 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl pyrimidin-1-yl) benzoyl chloride is characterized as follows: 1H-NMR (600 MHz, DMSO), data were as follows, delta 8.544 (d, J=7.6 Hz,1H, ar), 8.072 (d, J=9.6 Hz,1H, ar), 6.876 (s, 1H, CH), 3.984 (s, 3H, -CH 3). 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl pyrimidin-1-yl) benzoyl chloride (1.0 g,0.0026 mol) was dissolved in 20mL of dichloromethane to prepare solution A. The 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoic acid is shown as a formula (IV), the 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoyl chloride is shown as a formula (V),
(2) Methyl 3-hydroxybenzoate (0.4200 g,0.0027 mol) was dissolved in 5mL of methylene chloride, added to the prepared acid chloride, reacted for two minutes, then added with 0.4mL (0.2912, 0.0029 mol) of triethylamine, and reacted at room temperature for 5 hours; washing twice with dilute hydrochloric acid after the reaction is finished, separating by adopting a column chromatography, and drying to obtain white solid methyl 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidine-1 (6H) -yl) benzoate with the yield of 88%.
Nuclear magnetic resonance hydrogen spectrum characterization: 1H-NMR (500 MHz, CDCl 3), data were as follows, delta: 8.16 (d, 1H, ph-H), 8.06 (d, 1H, ph-H), 7.90 (s, 2H, ph-H), 7.54 (d, 1H, ph-H), 7.50 (t, 1H, ph-H), 7.46 (d, 1H, ph-H), 6.42 (s, 1H, CH), 3.95 (s, 3H, CH 3), 3.61 (s, 3H, CH 3), ESI [ M+Na ] +m/z 523.02924.
Example 2
The preparation method of uracil benzene ring ester compound shown in compound number 17 in table 1 comprises the following steps:
(1) 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoic acid (1.0 g,0.0026 mol) was added to thionyl chloride, heated at room temperature under reflux for 6h, and dried by spinning to give the desired product 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoyl chloride (0.8387 g,0.0022 mol) in 84% yield. The nuclear magnetic resonance hydrogen spectrum of the 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl pyrimidin-1-yl) benzoyl chloride is characterized as follows: 1H-NMR (400 MHz, DMSO), data were as follows, delta 8.544 (d, J=7.6 Hz,1H, ar), 8.072 (d, J=9.6 Hz,1H, ar), 6.876 (s, 1H, CH), 3.984 (s, 3H, -CH 3).
(2) Methyl 2-hydroxyphenylacetate (0.4540 g,0.0027 mol) was dissolved in 5mL of methylene chloride, and added to the solution A, followed by reaction for two minutes by addition of 0.4mL (0.2912, 0.0029 mol) of triethylamine, and reaction at room temperature for 6 hours; washing twice with dilute hydrochloric acid after the reaction is finished, mixing and washing with saturated sodium bicarbonate and saturated sodium chloride solution, separating by column chromatography, and drying to obtain dark yellow solid 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidine-1 (6H) -yl) benzoic acid-2-hydroxyphenylacetic acid methyl ester shown in formula (1) with 89% yield.
Example 3
The preparation method of uracil benzene ring ester compound shown in compound number 40 in table 1 comprises the following steps:
(1) 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoic acid (1.0 g,0.0026 mol) was added to thionyl chloride, heated at room temperature under reflux for 6h, and dried by spinning to give the desired product 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl-pyrimidin-1-yl) benzoyl chloride (0.8387 g,0.0022 mol) in 84% yield. The nuclear magnetic resonance hydrogen spectrum of the 2-chloro-4-fluoro-5- (1, 2,3, 6-tetrahydro-2, 6-dioxo-4-trifluoromethyl pyrimidin-1-yl) benzoyl chloride is characterized as follows: 1H-NMR (400 MHz, DMSO), data were as follows, delta 8.544 (d, J=7.6 Hz,1H, ar), 8.072 (d, J=9.6 Hz,1H, ar), 6.876 (s, 1H, CH), 3.984 (s, 3H, -CH 3).
(2) Ethyl 2- (2-hydroxyphenoxy) acetate (0.5460 g,0.0027 mol) was dissolved in 5mL of methylene chloride, which was added to the prepared acid chloride, and after two minutes of reaction, 0.4mL (0.2912, 0.0029 mol) of triethylamine was added to react for 4 hours at room temperature; washing twice with dilute hydrochloric acid after the reaction is finished, mixing and washing with saturated sodium bicarbonate and saturated sodium chloride solution, separating by column chromatography, and drying to obtain light white solid ethyl-2- (2-hydroxyphenoxy) acetate 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidine-1 (6H) -yl) benzoate with the yield of 89%.
Nuclear magnetic resonance hydrogen spectrum characterization: 1H-NMR (500 MHz, CDCl 3), data were as follows, delta: 8.37 (d, 1H, ph-H), 7.44 (d, 1H, ph-H), 7.24 (M, 2H, ph-H), 7.07 (t, 1H, ph-H), 6.93 (t, 1H, ph-H), 6.40 (s, 1H, CH), 4.63 (s, 2H, CH 2), 4.20 (M, 3H, CH 3), 3.60 (s, 3H, CH 3), 1.25 (t, 3H, CH 3), ESI [ M+Na ] +m/z 567.05545.
In the embodiment of the invention, uracil benzene ring ester compounds shown by the numbers of other compounds in the table 1 can be prepared by correspondingly adjusting the preparation method according to the preparation method described in the above examples; this embodiment will not be discussed in any great detail. Equivalent variations from the claims are intended to be covered by the invention.
Effect examples
Part of the compounds in the table 1 are subjected to a test for determining the herbicidal activity of various pests, and the herbicidal activity of the target compounds is determined by adopting a post-seedling stem and leaf treatment test method, wherein the test steps comprise:
(1) Loading soil without application into flowerpot, sowing, germinating, growing, spraying stem and leaf after dicotyledonous leaves grow to two leaves and one heart, monocotyledonous leaves grow to 2-3 leaves, dissolving the compound with small amount of organic solvent, adding small amount of emulsifying agent, diluting with water to obtain solution containing the compound, comparing with commercial compound saflufenacil (comparison compound), wherein saflufenacil is shown as formula (VI),
(2) Naturally growing plants under laboratory conditions, and supplementing water to the potted plants every day; the results of the investigation after 15 days of treatment with the agent are shown in table 3, wherein the herbicide scoring criteria are shown in table 2; the test targets in this experiment selected common gramineae weeds: barnyard grass, moleplant seed, and broadleaf weeds: amaranth and purslane.
Table 2: herbicide scoring criteria
Table 3: table 1 comparative table of herbicidal activity and crop safety scores of partial aryluracil benzofurans and control compounds
Note that: the compound numbers correspond to Table 1
The result shows that the aryl uracil benzene ring ester compound provided by the invention has higher weeding activity on gramineae and broadleaf grass; the existing saflufenacil has weeding activity on broadleaf grass and poor effect on gramineous weeds; therefore, the aryl uracil benzene ring ester compound provided by the invention has wide weed removal range and high-efficiency weeding activity. Meanwhile, aryl uracil benzene ring ester compounds have better safety on cabbages.
While the preferred embodiments have been described in detail, the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the scope of the present invention by those skilled in the art in light of the present application.

Claims (10)

1. Uracil benzene ring ester compound shown as formula (I):
in the formula (I), R 1 、R 2 Each independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl or C1-C8 alkynyl substituted by C1-C8 alkoxycarbonyl.
2. The uracil phenyl ester compound according to claim 1, wherein R is 3 Is C1-C4 alkoxycarbonyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkyl, C1-C4 alkoxycarbonyl-substituted C1-C8 alkoxy, C1-C4 alkoxycarbonyl-substituted C2-C8 alkenyl or C1-C4 alkoxycarbonyl-substituted C2-C8 alkynyl.
3. The uracil phenyl ester compound according to claim 2, wherein R is 3 Is C1-C2 alkoxycarbonyl, C1-C2 alkoxycarbonyl-substituted C1-C4 alkyl, C1-C2 alkoxycarbonyl-substituted C1-C2 alkoxy, C1-C2 alkoxycarbonyl-substituted C2-C4 alkenyl or C1-C2 alkoxycarbonyl-substituted C2-C4 alkynyl.
4. The uracil phenyl ester compound according to claim 1, wherein R is 1 Is a C1-C4 perfluoroalkyl group; the R is 2 Is C1-C4 alkyl; the X, Y is halogen.
5. The uracil phenyl ester compound according to claim 4, wherein R is 1 Is trifluoromethyl; the R is 2 Methyl or ethyl; the X, Y groups are each independently selected from fluorine or chlorine.
6. The preparation method of uracil benzene ring ester compound is characterized by comprising the following steps:
providing a compound A shown as a formula (II) and a compound B shown as a formula (III),
wherein R is 1 、R 2 Each independently selected from hydrogen, amino, C1-C4 alkyl or C1-C4 haloalkyl;
x, Y are each independently selected from hydrogen, halogen or cyano;
z is selected from oxygen atom or sulfur atom;
R 3 is C1-C8 alkoxycarbonyl, C1-C8 alkyl substituted by C1-C8 alkoxycarbonyl, C1-C8 alkoxy substituted by C1-C8 alkoxycarbonyl, C2-C8 alkenyl substituted by C1-C8 alkoxycarbonyl or C2-C8 alkynyl substituted by C1-C8 alkoxycarbonyl;
mixing the compound A and the compound B, adding a catalyst for reaction, collecting a solid product after the reaction is finished, purifying to obtain uracil benzene ring ester compounds shown as a formula (I),
7. the method for producing uracil phenyl ester compound according to claim 6, wherein the reaction temperature of the reaction is 0 ℃ to 160 ℃.
8. The method for producing uracil benzene ring ester compound according to claim 6 or 7, wherein the reaction time of the reaction is 2h to 15h.
9. A pesticidal composition, which comprises an active ingredient comprising the uracil phenyl ester compound according to any one of claims 1 to 5 or an agropharmaceutically acceptable salt thereof or the uracil phenyl ester compound prepared by the preparation method of the uracil phenyl ester compound according to any one of claims 6 to 8 or an agropharmaceutically acceptable salt thereof; the mass percentage of the active components in the pesticide composition is 1-99%.
10. Use of the uracil phenyl ester compound according to any of claims 1-5 or the pesticide composition according to claim 9 in herbicides or defoliants.
CN202311390249.3A 2023-10-25 2023-10-25 Uracil benzene ring ester compound, preparation method thereof and pesticide composition Pending CN117534624A (en)

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