WO2020237823A1 - 一种芳基尿嘧啶类化合物及其制备方法和农药组合物 - Google Patents

一种芳基尿嘧啶类化合物及其制备方法和农药组合物 Download PDF

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WO2020237823A1
WO2020237823A1 PCT/CN2019/098712 CN2019098712W WO2020237823A1 WO 2020237823 A1 WO2020237823 A1 WO 2020237823A1 CN 2019098712 W CN2019098712 W CN 2019098712W WO 2020237823 A1 WO2020237823 A1 WO 2020237823A1
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group
substituent group
compound
substituted
aryluracil
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PCT/CN2019/098712
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English (en)
French (fr)
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王明良
阎思彤
尹春慧
何雅慧
谢晗鑫
常超凡
朱才镇
徐坚
马晨生
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深圳大学
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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
    • 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

Definitions

  • the invention relates to the technical field of organic compounds, in particular to an aryluracil compound, a preparation method thereof, and a pesticide composition.
  • weeds cause great losses to crop production every year.
  • the main method of controlling weeds is spraying herbicides.
  • herbicides such as glyphosate
  • a large number of weeds have developed resistance, especially weeds such as gooseweed and barnyard grass have developed into a dominant and vicious weed.
  • the present invention provides an aryluracil compound.
  • the aryluracil compound has high selectivity, broad weeding spectrum, and resistance to weeds, especially against malignant weeds such as gooseberry. It has good control effect, low toxicity to mammals, and small impact on crops.
  • the present invention provides an aryluracil compound represented by formula I:
  • R 1 and R 2 are independently selected from hydrogen, amino, alkyl or haloalkyl, and the number of carbon atoms of the alkyl group and the haloalkyl group is 1-4;
  • X and Y are independently selected from hydrogen, halogen or cyano
  • Z is selected from oxygen atom or sulfur atom
  • R 3 is a C 1 -C 8 alkyl group substituted by the first substituent group, a C 2 -C 8 alkenyl group substituted by the first substituent group or a C 2 group substituted by the first substituent group -C 8 alkynyl; the first substituent group includes hydroxy, nitro, amino or alkylamino;
  • R 3 is a C 1 -C 8 alkyl group substituted by a second substituent group, a C 2 -C 8 alkenyl group substituted by a second substituent group, or a C 2 -C group substituted by a second substituent group 8 Alkynyl;
  • the second substituent group includes hydroxy, nitro, amino, alkylamino or alkoxycarbonyl.
  • the first substituent groups of C 1 -C 8 alkyl radical comprising one or more of the first group simultaneously substituted with substituted C 1 -C 8 alkyl groups; e.g., if R 3
  • the substituted C 1 -C 8 alkyl group may have one, two or more hydroxyl groups.
  • the first substituent group may also be one at the same time Or more.
  • the C 1 -C 8 alkyl group substituted by the second substituent group can also be one or more at the same time.
  • R 3 is a C 2 -C 8 alkyl group substituted by a first substituent group, a C 2 -C 8 alkenyl group substituted by a first substituent group, or a first substituent group substituted C 2 -C 8 alkynyl group; the first substituent group includes a hydroxyl group, a nitro group, an amino group or an alkylamino group;
  • Z is a sulfur atom
  • R 3 is a C 2 -C 8 alkyl group substituted by a second substituent group , C 2 -C 8 alkenyl substituted by a second substituent group or C 2 -C 8 alkynyl substituted by a second substituent group;
  • the second substituent group includes hydroxyl, nitro, amino, alkylamino or Alkoxycarbonyl.
  • the number of carbon atoms in the alkyl group or haloalkyl group independently selected from R 1 and R 2 is 1-4.
  • the alkyl group may be methyl, ethyl, propyl, isopropyl or butyl, etc.
  • the halogenated alkyl group is methyl, ethyl, propyl, isopropyl or butyl substituted by at least one halogen atom. Base etc.
  • the number of carbon atoms of the alkyl group and the haloalkyl group is 1-2.
  • the number of carbon atoms of the alkyl group and the halogenated alkyl group is 1-2.
  • the R 3 is a C 1 -C 4 alkyl group substituted by the first substituent group, or a C 2 -C 4 alkene substituted by the first substituent group Or C 2 -C 4 alkynyl substituted by the first substituent group.
  • the R 3 is a C 2 -C 4 alkyl group substituted by the first substituent group, or a C 2 -C 4 alkene substituted by the first substituent group Or C 2 -C 4 alkynyl substituted by the first substituent group.
  • the R 3 is a C 1 -C 4 alkyl group substituted by the second substituent group, or a C 2 -C 4 alkenyl group substituted by the second substituent group Or a C 2 -C 4 alkynyl group substituted by the second substituent group.
  • the R 3 is a C 2 -C 4 alkyl group substituted by the second substituent group, or a C 2 -C 4 alkenyl group substituted by the second substituent group Or a C 2 -C 4 alkynyl group substituted by the second substituent group.
  • the alkylamino group in the first substituent group is an alkylamino group having 1 to 3 carbon atoms; the alkylamino group in the second substituent group has a carbon number of The alkylamino group of 1-3, the alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 3 carbon atoms.
  • the alkoxycarbonyl group may include, but is not limited to, -COOCH 3 , -COOC 2 H 5 or -COOC 3 H 7 .
  • said R 1 is selected from hydrogen or C 1 -C 2 haloalkyl
  • said R 2 is selected from hydrogen or C 1 -C 2 alkyl
  • said X and Y are independently selected from Hydrogen or halogen
  • the R 3 is a C 1 -C 4 alkyl group substituted by at least one hydroxy, nitro, amino or alkylamino group, and at least one hydroxy, nitro, amino or alkyl group A C 2 -C 4 alkenyl substituted with an amino group, or a C 2 -C 4 alkynyl substituted with at least one hydroxy, nitro, amino or alkylamino group;
  • said R 3 is selected from C 1 -C 4 alkyl substituted by at least one hydroxyl, nitro, amino, alkoxycarbonyl or alkylamino, and at least one hydroxyl, nitro, amino, C 2 -C 4 alkenyl substituted with alkoxycarbonyl or alkylamino, or C 2 -C 4 alkynyl substituted with at least one hydroxy, nitro, amino, alkoxycarbonyl or alkylamino.
  • the R 1 is a trifluoromethyl group
  • the R 2 is a methyl group or an ethyl group
  • the X and Y are independently selected from fluorine or chlorine.
  • said R 1 is selected from hydrogen or trifluoromethyl
  • said R 2 is selected from hydrogen, methyl or ethyl
  • said X and Y are independently selected from hydrogen or halogen
  • the R 3 is selected from C 1 -C 4 alkyl substituted by at least one hydroxy, nitro or amino group, and C 2 -C substituted by at least one hydroxy, nitro or amino group. 4 Alkenyl, or C 2 -C 4 alkynyl substituted by at least one hydroxyl, nitro, or amino group;
  • the R 3 is selected from C 2 -C 4 alkyl substituted by at least one hydroxyl, nitro, amino or alkoxycarbonyl group, and at least one hydroxyl, nitro, amino or alkoxycarbonyl group A substituted C 2 -C 4 alkenyl group, or a C 2 -C 4 alkynyl group substituted with at least one hydroxy, nitro, amino or alkoxycarbonyl group.
  • the R 3 when the Z is an oxygen atom, the R 3 is selected from an ethyl group substituted by at least one hydroxyl group, a nitro group or an amino group; when the Z is a sulfur atom, the R 3 is selected from at least one hydroxyl group. , Nitro, amino or methoxycarbonyl substituted ethyl.
  • said R 1 is selected from hydrogen or trifluoromethyl
  • said R 2 is selected from hydrogen, methyl or ethyl
  • said X and Y are independently selected from hydrogen or halogen
  • the Z is an oxygen atom
  • the R 3 is selected from ethyl groups substituted by at least one hydroxyl, nitro or amino group
  • the Z is a sulfur atom
  • the R 3 is selected from the group consisting of at least one hydroxyl, nitro, Ethyl substituted with amino or methoxycarbonyl.
  • Each group on the aryluracil compound of the present invention has a great influence on the herbicidal activity of the entire aryluracil compound. Compared with traditional herbicide compounds, the aryluracil compounds of the present invention have stronger herbicidal effects and more outstanding selectivity.
  • the existing weeds are generally resistant to herbicides, the weeding spectrum of the existing herbicide compounds is narrow, and the inhibitory effect on goosegrass and other malignant weeds is very limited, even if the spraying amount per unit area is increased. Eliminate malignant weeds; even when the spray rate is increased, it will adversely affect beneficial crops, animals and soil.
  • the aryluracil compound of the present invention can effectively inhibit and remove malignant weeds with a small spray amount per unit area; the selection of each group in the structure of the aryluracil compound can be Greatly improve its selectivity and weeding spectrum range, so that it has high selectivity, wide weeding spectrum, and resistance to weeds, especially for goosegrass and other malignant weeds, and has a good control effect on lactation.
  • the present invention also provides a method for preparing aryluracil compounds, including the following steps:
  • R 1 and R 2 are independently selected from hydrogen, amino, alkyl or haloalkyl, and the number of carbon atoms of said alkyl and said haloalkyl is 1-4;
  • X and Y are independently selected from hydrogen, halogen or cyano
  • Z is selected from oxygen atom or sulfur atom
  • R 3 is a C 1 -C 8 alkyl group substituted by the first substituent group, a C 2 -C 8 alkenyl group substituted by the first substituent group or a C 2 group substituted by the first substituent group -C 8 alkynyl; the first substituent group includes hydroxy, nitro, amino or alkylamino;
  • R 3 is a C 1 -C 8 alkyl group substituted by a second substituent group, a C 2 -C 8 alkenyl group substituted by a second substituent group or a C 2 -C group substituted by a second substituent group 8 Alkynyl;
  • the second substituent group includes hydroxy, nitro, amino, alkylamino or alkoxycarbonyl;
  • the catalyst may be, but not limited to, an acid-bound catalyst.
  • the number of carbon atoms of the alkyl group and the haloalkyl group is 1-2.
  • the number of carbon atoms of the alkyl group and the halogenated alkyl group is 1-2.
  • R 3 is a C 1 -C 8 alkyl group substituted by a first substituent group, a C 2 -C 8 alkenyl group substituted by a first substituent group, or a first substituent group substituted C 2 -C 8 alkynyl group; the first substituent group includes a hydroxyl group, a nitro group, an amino group or an alkylamino group;
  • Z is a sulfur atom
  • R 3 is a C 1 -C 8 alkyl group substituted by a second substituent group , C 2 -C 8 alkenyl substituted by a second substituent group or C 2 -C 8 alkynyl substituted by a second substituent group;
  • the second substituent group includes hydroxyl, nitro, amino, alkylamino or Alkoxycarbonyl.
  • the R 3 is a C 1 -C 4 alkyl group substituted by the first substituent group, a C 2 -C 4 alkene substituted by the first substituent group Or C 2 -C 4 alkynyl substituted by the first substituent group.
  • the R 3 is a C 2 -C 4 alkyl group substituted by the first substituent group, or a C 2 -C 4 alkene substituted by the first substituent group Or C 2 -C 4 alkynyl substituted by the first substituent group.
  • the R 3 is a C 1 -C 4 alkyl group substituted by the second substituent group, or a C 2 -C 4 alkenyl group substituted by the second substituent group Or a C 2 -C 4 alkynyl group substituted by the second substituent group.
  • the R 3 is a C 2 -C 4 alkyl group substituted by the second substituent group, or a C 2 -C 4 alkenyl group substituted by the second substituent group Or a C 2 -C 4 alkynyl group substituted by the second substituent group.
  • the alkylamino group in the first substituent group is an alkylamino group having 1 to 3 carbon atoms; the alkylamino group in the second substituent group has a carbon number of The alkylamino group of 1-3, the alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 3 carbon atoms.
  • the R 1 is trifluoromethyl, and the R 2 is methyl or ethyl; and X and Y are independently selected from fluorine or chlorine.
  • the R 3 when the Z is an oxygen atom, the R 3 is selected from an ethyl group substituted with at least one hydroxyl, nitro or amino group; when the Z is a sulfur atom, the R 3 is selected from the group consisting of at least one hydroxyl group. , Nitro, amino or methoxycarbonyl substituted ethyl.
  • the preparation method described in the second aspect of the present invention is simple and convenient, has low pollution and high yield, and the preparation method can be applied to industrial production.
  • the aryluracil compound prepared by the preparation method of the present invention has high selectivity, low dosage, wide weeding spectrum, and resistance to weeds, especially good control of malignant weeds such as goosegrass It has the advantages of low toxicity to mammals and small impact on crops.
  • the present invention also provides a pesticide composition, which comprises the aryluracil compound as described in the first aspect of the present invention or an agrochemically acceptable salt thereof.
  • the pesticide composition may also include an aryluracil compound or a pesticide acceptable salt thereof prepared by the method for preparing an aryluracil compound according to the second aspect of the present invention.
  • the mass percentage of the aryluracil compound is 0.1% to 99.9%.
  • the pesticide composition further includes a pesticide-acceptable formulation adjuvant.
  • the formulation adjuvant includes liquid carriers, solid carriers, emulsifiers, surfactants, binders, thickeners, colorants, spreading agents, antifreeze agents, anti-caking agents, disintegrating agents and anti-freezing agents.
  • the decomposition agents include liquid carriers, solid carriers, emulsifiers, surfactants, binders, thickeners, colorants, spreading agents, antifreeze agents, anti-caking agents, disintegrating agents and anti-freezing agents.
  • the pesticide composition can also be added with other components with herbicidal effects such as glyphosate, glufosinate-ammonium.
  • the pesticide composition can be used as a herbicide and/or defoliant.
  • the mass percentage of the aryluracil compound is 0.1% to 99.9%.
  • the mass percentage of the aryluracil compound is 0.1%-40.0%.
  • the pesticide composition of the present invention When used as a herbicide, it can have both high selectivity, low dosage, wide weeding spectrum, and resistance to weeds, and has a good control effect on malignant weeds such as goosegrass. advantage.
  • the mass percentage of the aryluracil compound is 0.1% to 99.9%.
  • the mass percentage of the aryluracil compound is 20.0%-50.0%.
  • the defoliating agent of the present invention can be applied to the defoliation requirements of various plants.
  • the defoliating agent is used to defoliate cotton crops and exhibits a significant defoliation effect.
  • the pesticide composition can be used by spraying or by other methods.
  • the raw materials and other chemical reagents used in the embodiments of the present invention are all commercially available products.
  • the present invention provides an aryluracil compound as shown in formula I:
  • R 1 and R 2 are independently selected from hydrogen, amino, alkyl or haloalkyl, and the number of carbon atoms of said alkyl and said haloalkyl is 1-4;
  • X and Y are independently selected from hydrogen, halogen or cyano
  • Z is selected from oxygen atom or sulfur atom
  • R 3 is a C 1 -C 8 alkyl group substituted by the first substituent group, a C 2 -C 8 alkenyl group substituted by the first substituent group or a C 2 group substituted by the first substituent group -C 8 alkynyl; the first substituent group includes hydroxy, nitro, amino or alkylamino;
  • R 3 is a C 1 -C 8 alkyl group substituted by a second substituent group, a C 2 -C 8 alkenyl group substituted by a second substituent group or a C 2 -C group substituted by a second substituent group 8 Alkynyl;
  • the second substituent group includes hydroxy, nitro, amino, alkylamino or alkoxycarbonyl.
  • aryluracil compounds are shown in Table 1, but the aryluracil compounds of the present invention are not limited to all the compounds in Table 1.
  • the preparation method of the aryluracil compound shown in compound number 4 in Table 1 The preparation method of the aryluracil compound shown in compound number 4 in Table 1:
  • the aryluracil compound shown in compound number 4 is as shown in formula (1),
  • the preparation process includes:
  • the aryluracil compound represented by compound number 8 is represented by formula (2),
  • the preparation method includes:
  • the aryluracil compound represented by compound number 12 is represented by formula (3),
  • the preparation method includes:
  • step (2) Add ethyl acetate or dichloromethane to the crude product obtained in step (1), filter, wash with saturated sodium chloride and saturated sodium bicarbonate solution (1:1), wash three times, separate, and chlorinate with anhydrous The calcium was dried, filtered, and spin-dried to obtain a pale yellow powdery solid (0.06 g, 0.00014 mol, yield 14.2%) as shown in formula (3).
  • the aryluracil compound represented by compound number 16 is represented by formula (4),
  • the preparation method includes:
  • the aryluracil compound represented by compound number 24 is represented by formula (5),
  • the preparation method includes:
  • reaction formula (A1) including:
  • the aryluracil compounds shown in the other compound numbers in Table 1 can be prepared by corresponding adjustments with reference to the preparation methods described in the foregoing examples; this embodiment will not be discussed too much.
  • the post-emergence stem and leaf treatment experiment method was used to determine the herbicidal activity of the target compound
  • control group is the commercial compound saflufenacil (comparative compound 1) And fluprofenic-ethyl (control compound 2), wherein the control compound 1 (fenflufentrazone) is represented by formula (6), and the control compound 2 (fluprofenacet) is represented by formula (7),
  • Table 3 Comparison of herbicidal activity scores of some aryluracil compounds in Table 1 and control compounds
  • Table 4 Comparison of herbicidal activity and crop damage scores of some aryluracil compounds in Table 1
  • the aryluracil compound No. 4 which is almost harmless to corn and wheat, was further tested for the treatment of stems and leaves.
  • the untreated soil into the flower pot add water and wait for the soil to be completely moistened, sow the target crop seeds wheat and corn seeds into the pot, the plants will grow naturally under laboratory conditions, and the pot will be supplemented with water every day. It grows to 3-4 leaf stage, and sprays stems and leaves at a dose of 11.25-22.5 g/ha.
  • the indoor safety test found that the No. 4 aryluracil compound has good safety to corn and wheat.
  • the results show that the aryluracil compounds provided by the present invention have high herbicidal activity on both grasses and broadleaf grasses; while the existing saflufenacil has herbicidal activity on broadleaf grasses, and has herbicidal activity against grass weeds.
  • the effect is poor; therefore, the aryluracil compound provided by the present invention has a wide range of weed removal and has high herbicidal activity.
  • the aryluracil compounds provided by the invention have more prominent herbicidal activity on weeds such as gooseweed which are difficult to control.
  • the compound shown in Table 1 provided by the present invention for stem and leaf treatment has broad-spectrum activity on goosegrass and other vicious grass weeds and broadleaf weeds, so it can be used as a non-selective herbicide as a stem and leaf treatment.
  • the aryluracil compound of compound No. 4 is almost harmless to corn and wheat, and has excellent herbicidal activity to gramineous and broadleaf grasses, and can be used as crop cultivation. Selective herbicide use.
  • the solubility of the aryluracils of compound numbers 4 and 8 is about 0.2 g/l at 25°C, which is greater than the solubility of the control compound (2) by 0.1 g/l, and the aryluracils of compound number 4 have Better water solubility and bioavailability, especially the herbicidal activity of goosegrass is higher than the control compound (2).
  • the compound represented by the compound structure (I) of the present invention has very high herbicidal activity, which can greatly reduce the dosage of medicaments and help reduce environmental pollution problems.

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Abstract

一种如式(Ⅰ)所示的芳基尿嘧啶类化物：其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤代烷基的碳原子数为1-4；X、Y独立地选自氢、卤素或氰基；Z选自氧原子或硫原子；其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。该芳基尿嘧啶类化物选择性高、除草谱广，对牛筋草等恶性杂草防除效果好。还提供其制备方法和农药组合物。

Description

一种芳基尿嘧啶类化合物及其制备方法和农药组合物
本申请要求2019年5月31日提交中国专利局的，申请号为201910469994.4，发明名称为“一种芳基尿嘧啶类化合物及其制备方法和农药组合物”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及有机化合物技术领域，特别涉及一种芳基尿嘧啶类化合物及其制备方法和农药组合物。
背景技术
由于与农作物争光和争肥水，杂草每年给农作物生产造成很大损失，目前防治杂草的主要方法是喷洒除草剂。然而，随着除草剂(例如草甘膦)的广泛应用，大量的杂草已产生抗性，尤其是牛筋草、稗草等杂草已发展成为一种优势杂草和恶性杂草。
现有市场上存在多种除草剂一般作为非选择性除草剂，且普遍存在防除效果较差，去除杂草范围窄和高剂量用药等特点，特别是对牛筋草、稗草等恶性杂草的杀伤效果差。同时，作为选择性除草剂时常对农作物的生长产生不利影响，造成巨大经济损失。
因此，有必要提供一种选择性高、除草谱广、杂草不易产生抗性，尤其对牛筋草等恶性杂草具有较好的防除效果的新型除草化合物。
发明内容
基于上述技术问题，本发明提供了一芳基尿嘧啶类化合物，该芳基尿嘧啶类化合物具有选择性高、除草谱广、杂草不易产生抗性，尤其对牛筋草等恶性 杂草具有较好的防除效果，且对哺乳动物毒性低，对农作物影响小等优点。
第一方面，本发明提供了一种如式Ⅰ所示的芳基尿嘧啶类化合物：
Figure PCTCN2019098712-appb-000001
其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤代烷基的碳原子数为1-4；
X、Y独立地选自氢、卤素或氰基；
Z选自氧原子或硫原子；
其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；
当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。
本发明实施方式中，所述第一取代基团取代的C 1-C 8烷基包括一个或多个所述第一取代基团同时取代的C 1-C 8烷基；例如，当R 3所述第一取代基团为羟基时，所述取代的C 1-C 8烷基上可以有一个、两个或多个羟基。
类似地，所述第一取代基团取代的C 1-C 8烯基和所述第一取代基团取代的C 2-C 8炔基中，所述第一取代基团也可以同时为一个或多个。
类似地，所述第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基中，所述第二取代基团也可以同时为一个或多个。
可选地，当Z为氧原子，R 3为第一取代基团取代的C 2-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；当Z为硫原子，R 3为第二取代基团取代的C 2-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。
本实施方式中，R 1、R 2独立地选自的烷基或卤代烷基中的碳原子数为1-4。例如，所述烷基可以为甲基、乙基、丙基、异丙基或丁基等；所述卤代烷基至少被一个卤素原子取代的甲基、乙基、丙基、异丙基或丁基等。
可选地，所述R 1和所述R 2中，所述烷基和所述卤代烷基的碳原子数为1-2。例如，所述烷基和所述卤代烷基的碳原子数为1-2。
可选地，当所述Z为氧原子时，所述R 3为所述第一取代基团取代的C 1-C 4烷基、所述第一取代基团取代的C 2-C 4烯基或所述第一取代基团取代的C 2-C 4炔基。
可选地，当所述Z为氧原子时，所述R 3为所述第一取代基团取代的C 2-C 4烷基、所述第一取代基团取代的C 2-C 4烯基或所述第一取代基团取代的C 2-C 4炔基。
可选地，当所述Z为硫原子，所述R 3为所述第二取代基团取代的C 1-C 4烷基、所述第二取代基团取代的C 2-C 4烯基或所述第二取代基团取代的C 2-C 4炔基。
可选地，当所述Z为硫原子，所述R 3为所述第二取代基团取代的C 2-C 4烷基、所述第二取代基团取代的C 2-C 4烯基或所述第二取代基团取代的C 2-C 4炔基。
可选地，所述第一取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基；所述第二取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基，所述烷氧羰基为碳原子数为1-3的烷氧羰基。
例如，所述烷氧羰基可以但不限于包括-COOCH 3、-COOC 2H 5或-COOC 3H 7。
例如，本发明一实施方式中，所述R 1选自氢或C 1-C 2卤代烷基；所述R 2选自氢或C 1-C 2烷基；所述X、Y独立地选自氢或卤素；
其中，当所述Z为氧原子，所述R 3为至少被一个羟基、硝基、氨基或烷基氨基取代的C 1-C 4烷基，至少被一个羟基、硝基、氨基或烷基氨基取代的C 2-C 4烯基，或至少被一个羟基、硝基、氨基或烷基氨基取代的C 2-C 4炔基；
当Z选自硫原子，所述R 3选自至少被一个羟基、硝基、氨基、烷氧羰基或烷基氨基取代的C 1-C 4烷基，至少被一个羟基、硝基、氨基、烷氧羰基或烷基氨基取代的C 2-C 4烯基，或至少被一个羟基、硝基、氨基、烷氧羰基或烷基氨基取代的C 2-C 4炔基。
可选地，所述R 1为三氟甲基，所述R 2为甲基或乙基；所述X、Y独立地选自氟或氯。
例如，本发明另一实施方式中，所述R 1选自氢或三氟甲基，所述R 2选自氢、甲基或乙基；所述X、Y独立地选自氢或卤素；
其中，当所述Z为氧原子，所述R 3选自至少被一个羟基、硝基或氨基取代的C 1-C 4烷基，至少被一个羟基、硝基或氨基取代的C 2-C 4烯基，或至少被一个羟基、硝基、氨基取代的C 2-C 4炔基；
当所述Z为硫原子，所述R 3选自至少被一个羟基、硝基、氨基或烷氧羰基取代的C 2-C 4烷基，至少被一个羟基、硝基、氨基或烷氧羰基取代的C 2-C 4烯基，或至少被一个羟基、硝基、氨基或烷氧羰基取代的C 2-C 4炔基。
可选地，当所述Z为氧原子，所述R 3选自至少被一个羟基、硝基或氨基取代的乙基；当所述Z为硫原子，所述R 3选自至少被一个羟基、硝基、氨基或甲氧羰基取代的乙基。
例如，本发明另一实施方式中，所述R 1选自氢或三氟甲基，所述R 2选自氢、甲基或乙基；所述X、Y独立地选自氢或卤素；当所述Z为氧原子，所述R 3选自至少被一个羟基、硝基或氨基取代的乙基；当所述Z为硫原子，所述R 3选自至少被一个羟基、硝基、氨基或甲氧羰基取代的乙基。
本发明所述芳基尿嘧啶类化合物上的每个基团对于整个所述芳基尿嘧啶类化合物的除草活性都具有很大的影响。本发明所述芳基尿嘧啶类化合物相比于传统的除草剂化合物，所述化合物具有更强的除草效果，且选择性更突出。
由于现有的杂草普遍对除草剂产生有抗性，现有除草剂化合物组分的除草谱范围窄，对于牛筋草等恶性杂草抑制作用十分有限，即使增加单位面积的喷洒量也无法消除恶性杂草；甚至当提高喷洒量时，对有益农作物、动物及土壤造成不利影响。而本发明所述芳基尿嘧啶类化合物，其可以在很少的单位面积的喷洒量下，也可以有效抑制并去除恶性杂草；该芳基尿嘧啶类化合物结构中各个基团的选择可以极大限度的提高其选择性和除草谱范围，使其具有选择性高、除草谱广、杂草不易产生抗性，尤其对牛筋草等恶性杂草具有较好的防除效果，且对哺乳动物毒性低，对农作物影响小等优点。
第二方面，本发明还提供了一种芳基尿嘧啶类化合物的制备方法，包括以下步骤：
(1)提供或制备如式Ⅱ所述的化合物A，以及提供或制备如式Ⅲ所述的化合物B，
Figure PCTCN2019098712-appb-000002
其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤 代烷基的碳原子数为1-4；
X、Y独立地选自氢、卤素或氰基；
Z选自氧原子或硫原子；
其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；
当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基；
(2)将所述化合物A和所述化合物B混合，然后添加催化剂进行反应，反应完毕后收集并纯化得到如式Ⅰ所示的芳基尿嘧啶类化合物，
Figure PCTCN2019098712-appb-000003
可选地，所述催化剂可以但不限于缚酸催化剂。
可选地，所述R 1和所述R 2中，所述烷基和所述卤代烷基的碳原子数为1-2。例如，所述烷基和所述卤代烷基的碳原子数为1-2。
可选地，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。
可选地，当所述Z为氧原子时，所述R 3为所述第一取代基团取代的C 1-C 4 烷基、所述第一取代基团取代的C 2-C 4烯基或所述第一取代基团取代的C 2-C 4炔基。
可选地，当所述Z为氧原子时，所述R 3为所述第一取代基团取代的C 2-C 4烷基、所述第一取代基团取代的C 2-C 4烯基或所述第一取代基团取代的C 2-C 4炔基。
可选地，当所述Z为硫原子，所述R 3为所述第二取代基团取代的C 1-C 4烷基、所述第二取代基团取代的C 2-C 4烯基或所述第二取代基团取代的C 2-C 4炔基。
可选地，当所述Z为硫原子，所述R 3为所述第二取代基团取代的C 2-C 4烷基、所述第二取代基团取代的C 2-C 4烯基或所述第二取代基团取代的C 2-C 4炔基。
可选地，所述第一取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基；所述第二取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基，所述烷氧羰基为碳原子数为1-3的烷氧羰基。
可选地，所述R 1为三氟甲基，所述R 2为甲基或乙基；所述X、Y独立地选自氟或氯。
可选地，当所述Z为氧原子，所述R 3选自至少被一个羟基、硝基或氨基取代的乙基；当所述Z为硫原子，所述R 3选自至少被一个羟基、硝基、氨基或甲氧羰基取代的乙基。
本发明第二方面所述制备方法精简方便，污染少、产率高，所述制备方法可以适用于工业化生产。由本发明所述制备方法制得的所述芳基尿嘧啶类化合物具有选择性高、用量低、除草谱广、杂草不易产生抗性，尤其对牛筋草等恶性杂草具有较好的防除效果，且对哺乳动物毒性低，对农作物影响小等优点。
第三方面，本发明还提供了一种农药组合物，包括如本发明第一方面所述的芳基尿嘧啶类化合物或其农药学上可接受的盐。
本发明实施方式中，所述农药组合物还可以包括如本发明第二方面所述芳基尿嘧啶类化合物的制备方法制得的芳基尿嘧啶类化合物或其农药学上可接受的盐。
可选地，所述农药组合物中，所述芳基尿嘧啶类化合物的质量百分含量为0.1％-99.9％。
可选地，所述农药组合物还包括农药学上可接受的配制佐剂。可选地，所述配制佐剂包括液体载体、固体载体、乳化剂、表面活性剂、粘合剂、增稠剂、着色剂、展开剂、防冻剂、防结块剂、崩解剂和抗分解剂中的一种或多种。
可选地，所述农药组合物还可以添加草甘膦、草铵膦等其他具有除草功效的组分。
本发明实施方式中，所述农药组合物可用于除草剂和/或落叶剂。
其中，所述农药组合物可用于除草剂时，所述芳基尿嘧啶类化合物的质量百分含量为0.1％-99.9％。
可选地，所述农药组合物可用于除草剂时，所述芳基尿嘧啶类化合物的质量百分含量为0.1％-40.0％。
本发明所述农药组合物用于除草剂时，可以兼具选择性高、用量低、除草谱广、杂草不易产生抗性，尤其对牛筋草等恶性杂草具有较好的防除效果等优点。
可选地，所述农药组合物可用于落叶剂时，所述芳基尿嘧啶类化合物的质量百分含量为0.1％-99.9％。
进一步地，可选地，所述农药组合物可用于落叶剂时，所述芳基尿嘧啶类化合物的质量百分含量为20.0％-50.0％。
本发明所述落叶剂可以适用于各种植物的落叶需求，例如，所述落叶剂被采用来使棉花作物落叶，且表现出了明显的落叶效果。
可选地，所述农药组合物可通过喷洒方式使用，或通过其他方式进行使用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
若无特别说明，本发明实施例所采用的原料及其它化学试剂皆为市售商品。
本发明提供了一种如式Ⅰ所示的芳基尿嘧啶类化合物：
Figure PCTCN2019098712-appb-000004
其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤代烷基的碳原子数为1-4；
X、Y独立地选自氢、卤素或氰基；
Z选自氧原子或硫原子；
其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；
当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。
具体地，部分所述芳基尿嘧啶类化合物参见表1，但本发明所述芳基尿嘧啶类化合物不仅限于表1中的所有化合物。
表1：具有如式Ⅰ所示的化学结构式的芳基尿嘧啶类化合物：
化合物编号 R 1 R 2 Z R3 X Y
1 CF 3 CH 3 O CH 2CH 2OH H H
2 CF 3 CH 3 O CH 2CH 2OH H Cl
3 CF 3 CH 3 O CH 2CH 2OH Cl Cl
4 CF 3 CH 3 O CH 2CH 2OH F Cl
5 CF 3 CH 3 O CH 2CH 2NO 2 H H
6 CF 3 CH 3 O CH 2CH 2NO 2 H Cl
7 CF 3 CH 3 O CH 2CH 2NO 2 Cl Cl
8 CF 3 CH 3 O CH 2CH 2NO 2 F Cl
9 CF 3 CH 3 O CH 2CH 2CH 2NH 2 H H
10 CF 3 CH 3 O CH 2CH 2CH 2NH 2 H Cl
11 CF 3 CH 3 O CH 2CH 2CH 2NH 2 Cl Cl
12 CF 3 CH 3 O CH 2CH 2CH 2NH 2 F Cl
13 CF 3 CH 3 O CH 2CH 2N(CH 3) H H
14 CF 3 CH 3 O CH 2CH 2N(CH 3) H Cl
15 CF 3 CH 3 O CH 2CH 2N(CH 3) Cl Cl
16 CF 3 CH 3 O CH 2CH 2N(CH 3) F Cl
17 CF 3 CH 3 O CH 2CH(OH)CH 2(OH) H H
18 CF 3 CH 3 O CH 2CH(OH)CH 2(OH) H Cl
19 CF 3 CH 3 O CH 2CH(OH)CH 2(OH) Cl Cl
20 CF 3 CH 3 O CH 2CH(OH)CH 2(OH) F Cl
21 CF 3 CH 3 S CH 2COOCH 3 H H
22 CF 3 CH 3 S CH 2COOCH 3 H Cl
23 CF 3 CH 3 S CH 2COOCH 3 Cl Cl
24 CF 3 CH 3 S CH 2COOCH 3 F Cl
25 CF 3 CH 3 S CH 2COOC 2H 5 H H
26 CF 3 CH 3 S CH 2COOC 2H 5 H Cl
27 CF 3 CH 3 S CH 2COOC 2H 5 Cl Cl
28 CF 3 CH 3 S CH 2COOC 2H 5 F Cl
29 CF 3 CH 3 S CH 2CH 2OH H H
30 CF 3 CH 3 S CH 2CH 2OH H Cl
31 CF 3 CH 3 S CH 2CH 2OH Cl Cl
32 CF 3 CH 3 S CH 2CH 2OH F Cl
33 CF 3 CH 3 S CH 2CH 2NO 2 H H
34 CF 3 CH 3 S CH 2CH 2NO 2 H Cl
35 CF 3 CH 3 S CH 2CH 2NO 2 Cl Cl
36 CF 3 CH 3 S CH 2CH 2NO 2 F Cl
37 CF 3 CH 3 S CH 2CH 2CH 2NH 2 H H
38 CF 3 CH 3 S CH 2CH 2CH 2NH 2 H Cl
39 CF 3 CH 3 S CH 2CH 2CH 2NH 2 Cl Cl
40 CF 3 CH 3 S CH 2CH 2CH 2NH 2 F Cl
41 CF 3 CH 3 S CH 2CH 2N(CH 3) H H
42 CF 3 CH 3 S CH 2CH 2N(CH 3) H Cl
43 CF 3 CH 3 S CH 2CH 2N(CH 3) Cl Cl
44 CF 3 CH 3 S CH 2CH 2N(CH 3) F Cl
45 CF 3 CH 3 S CH 2CH(OH)CH 2(OH) H H
46 CF 3 CH 3 S CH 2CH(OH)CH 2(OH) H Cl
47 CF 3 CH 3 S CH 2CH(OH)CH 2(OH) Cl Cl
48 CF 3 CH 3 O CH 2CH 2OH F CN
49 CF 3 CH 3 O CH 2CH 2NO 2 F CN
50 CF 3 CH 3 O CH 2CH 2NH 2 F CN
51 CF 3 CH 3 O CH 2CH 2N(CH 3) F CN
52 CF 3 CH 3 S CH 2CH 2OH F CN
53 CF 3 CH 3 S CH 2CH 2NO 2 F CN
54 CF 3 CH 3 S CH 2CH 2NH 2 F CN
55 CF 3 CH 3 S CH 2CH 2N(CH 3) F CN
56 CF 3 CH 3 S CH 2COOCH 3 F CN
57 CF 3 CH 3 O CH 2CH＝CHOH F Cl
58 CF 3 CH 3 O CH 2CH≡COH F Cl
59 CF 3 CH 3 O CH 2CH＝CHNO 2 F Cl
60 CF 3 CH 3 O CH 2CH≡CNO 2 F Cl
61 CF 3 CH 3 O CH 2CH 2NHCH 3 F Cl
实施例1
表1中化合物编号4所示的芳基尿嘧啶类化合物的制备方法：所述化合物编号4所示的芳基尿嘧啶类化合物的如式(1)所示，
Figure PCTCN2019098712-appb-000005
其制备过程包括：
(1)将2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸(1.0g，0.0026mol)加入到氯化亚砜中，室温下加热回流6h，旋干得到目标产物2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(0.8387g，0.0022mol)，产率为84％。所述2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯的核磁共振氢谱表征为： 1H-NMR(600MHz,DMSO)，数据如下，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,-CH 3)。取2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(1.0g，0.0026mol)溶于20mL的二氯甲烷中，配成溶液A，所述2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸如式Ⅳ所示，所述2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯式Ⅴ所示，
Figure PCTCN2019098712-appb-000006
(2)取乙二醇(0.4836g，0.0078mol)，加入吡啶(0.2037g，0.0025mol)用磁力搅拌器搅拌半小时，然后缓慢滴加溶液A，在常温下反应2h；待反应完毕后采用柱色谱法进行分离，干燥可得如式(1)所示的浅黄色固体2-羟基乙基-2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸酯(0.3960g，0.0009mol，产率40％)。
核磁共振氢谱表征： 1H-NMR(600MHz,CDCl 3)，数据如下，δ:7.946(d,J＝7.2Hz,1H,Ar),7.424(d,J＝8.0Hz,1H,Ar),6.396(s,1H,Ar),4.476(t,J＝6.4Hz,6.4Hz, 2H,CH),3.961(t,J＝6.4Hz,6.4Hz,2H,CH),3.589(s,3H,Ar)，ESI[M+H] +m/z411.0369。
实施例2
表1中化合物编号8所示的芳基尿嘧啶类化合物的制备方法：
所述化合物编号8所示的芳基尿嘧啶类化合物的如式(2)所示，
Figure PCTCN2019098712-appb-000007
其制备方法包括：
(1)将2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸(1.0g，0.0026mol)加入到氯化亚砜中，室温下加热回流6h，旋干得到目标产物2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(0.8387g，0.0022mol)，产率为84％。所述2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯的核磁共振氢谱表征为：1H-NMR(400MHz,DMSO)，数据如下，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,-CH 3)。
(2)取2-硝基乙醇(0.0911g，0.0010mol)，2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(0.366g，0.0010mol)，加入30ml苯，磁力搅拌器搅拌下，回流24h；待反应完毕后，用饱和氯化钠与饱和碳酸氢钠溶液(1:1)，洗涤三次，分液，用无水硫酸镁干燥，过滤，旋干，真空干燥得淡黄色固体。待反应完毕后采用柱色谱法进行分离，干燥可得如式(2)所示的浅黄色固体2-硝基乙基-2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸酯(0.4135g，0.0009mol，产率94.2％)。
核磁共振氢谱表征： 1H-NMR(600MHz,CDCl 3)，数据如下，δ:7.85(d,J＝7.8Hz,1H,Ar),7.40(d,J＝8.4Hz,1H,Ar),6.39(s,1H,Ar),4.86(m,J＝6.0Hz,6.0Hz,2H,CH 2),4.73(m,J＝6.0Hz,6.0Hz,2H,CH 2),3.57(s,3H,CH 3)，ESI[M+H] +m/z 440.0267。
实施例3
表1中化合物编号12所示的芳基尿嘧啶类化合物的制备方法：
所述化合物编号12所示的芳基尿嘧啶类化合物的如式(3)所示，
Figure PCTCN2019098712-appb-000008
其制备方法包括：
(1)取2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸(0.366g，1mmol)与3-氨基丙醇(0.0751g，1mmol)混合，加入甲烷磺酸(1mL，15mmol)，氧化铝(0.27g，3mmol)作为催化剂，加热至80℃，回流1h。
(2)加入乙酸乙酯或二氯甲烷于步骤(1)所得粗产物，过滤，用饱和氯化钠与饱和碳酸氢钠溶液(1:1)，洗涤三次，分液，用无水氯化钙干燥，过滤，旋干得到如式(3)所示的淡黄色粉末状固体(0.06g，0.00014mol，产率14.2％)。
核磁共振氢谱表征： 1H-NMR(400MHz,CDCl 3)，数据如下，δ:7.83(d,J＝8.0Hz,1H,Ar)，7.36(d,J＝8.0Hz,1H,Ar)，6.37(s,1H,Ar)，5.35(t,2H,J＝4.0Hz，NH 2)，3.56(s,3H,CH 3)，2.22(t,2H,J＝8.0Hz，CH 2)，2.01(m,4H，CH 2CH 2)，ESI[M+H] +m/z 424.0679。
实施例4
表1中化合物编号16所示的芳基尿嘧啶类化合物的制备方法：
所述化合物编号16所示的芳基尿嘧啶类化合物的如式(4)所示，
Figure PCTCN2019098712-appb-000009
其制备方法包括：
(1)取2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(0.5010g，0.0013mol)溶于10mL的二氯甲烷中，配成溶液A。
(2)向N,N-二甲基乙醇胺(0.4836g，0.0078mol)中缓慢滴加溶液A，在常温下反应1h，洗涤后，干燥可得如式(4)所示的白色固体2-(二甲基氨基)乙基2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸酯(0.4090g，0.0009mol，产率72％)。
核磁共振氢谱表征： 1H-NMR(600MHz,CDCl 3)，数据如下，δ:7.968(d,J＝7.8Hz,1H,Ar)，7.402(d,J＝8.0Hz,1H,Ar)，6.389(s,1H,Ar)，4.476(t,J＝5.4Hz,6.0Hz,2H,CH)，3.580(s,3H,Ar)，2.768(t,J＝5.4Hz,6.0Hz,2H,CH)，2.368(s,6H,-N(CH 3) 2)，ESI[M+H] +m/z 438.0838。
实施例5
表1中化合物编号24所示的芳基尿嘧啶类化合物的制备方法：
所述化合物编号24所示的芳基尿嘧啶类化合物的如式(5)所示，
Figure PCTCN2019098712-appb-000010
其制备方法包括：
(1)取2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酰氯(1.0295g，0.0027mol)溶于20mL的二氯甲烷中，配成溶液A。
(2)向溶液A中加入巯基乙酸甲酯(0.5935g，0.0056mol)，三乙胺(0.3630g，0.0036mol)，在常温下反应2h，洗涤后，干燥可得如式(5)所示的浅黄色固体硫代乙酸甲酯-2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-4-三氟甲基嘧啶-1-基)苯甲酸酯(0.6864g，0.0015mol，产率56％)。
核磁共振氢谱表征： 1H-NMR(600MHz,DMSO)，数据如下，δ:8.077(d,J＝7.2Hz,1H,Ar)，7.953(d,J＝9.6Hz,1H,Ar)，6.622(s,1H,Ar)，4.052(s,2H,CH)，3.960(s,3H,Ar)，3.425(s,3H,-OCH 3)，ESI[M+H] +m/z 455.0085。
本发明实施方式中，所述制备方法中，所述2-氯-4-氟-5-(1,2,3,6-四氢-2,6-二氧-3-甲基-4-三氟甲基嘧啶-1-基)苯甲酸(Ⅳ)的制备过程可以为如下反应流程所述，所述反应流程参见如反应式(A1)，包括：
Figure PCTCN2019098712-appb-000011
本发明实施方式中，所述表1中其他化合物编号所示的芳基尿嘧啶类化合物可参照上述实施例所述的制备方法中进行相应调整制备获得；本实施方式中不做过多论述。
效果实施例1
所述芳基尿嘧啶类化合物除草活性的测定实验：
为有效证明本发明提供的新型的所述芳基尿嘧啶类化合物有益效果，现选取部分表1所述的芳基尿嘧啶类化合物进行除草活性的测定实验，实验大致步 骤包括：
采用苗后茎叶处理实验方法，测定目标化合物的除草活性；
(1)将未施用过药的土壤的装入花盆中，然后播种，进行发芽生长，待双子叶长至4-5叶期，单子叶长至4-5叶期，进行茎叶喷雾处理(在施用该化合物时，该化合物先用少量有机溶剂溶解后，加入少量的乳化剂，再用水进行稀释得到含有该化合物的溶液)，对照组为商品化合物苯嘧磺草胺(对照化合物1)和氟丙嘧草酯(对照化合物2)，其中，对照化合物1(苯嘧磺草胺)如式(6)所示，对照化合物2(氟丙嘧草酯)如式(7)所示，
Figure PCTCN2019098712-appb-000012
(2)植物在实验室条件下自然生长，每天对盆栽补水；药剂处理15天后调查结果参见表3，其中，除草剂评分标准参见表2所示；本实验中试验靶标选取常见的禾木科杂草：稗草、马唐、牛筋草，以及阔叶草杂草：苋菜、马齿苋。
表2：除草剂评分标准
Figure PCTCN2019098712-appb-000013
表3：表1中部分芳基尿嘧啶类化合物与对照化合物的除草活性评分对比表
Figure PCTCN2019098712-appb-000014
Figure PCTCN2019098712-appb-000015
Figure PCTCN2019098712-appb-000016
注：化合物编号与表1对应
效果实施例2
采用苗前土壤处理实验方法，测定目标化合物的除草活性和作物的安全性；
将未施用过药的土壤的装入花盆中，加水待土壤完全湿润后，分别将靶标杂草和作物种子播入盆内，每种杂草保证10-15粒种子，覆土1厘米，播种1天后进行药剂处理，待药液自然阴干后、放于室内按常规方法管理。药剂处理15天后调查结果参见表4。
表4：表1中部分芳基尿嘧啶类化合物除草活性和对作物破坏性评分对比表
Figure PCTCN2019098712-appb-000017
效果实施例3
对土壤处理时对玉米和小麦几乎无药害的编号4的芳基尿嘧啶类化合物做进一步的茎叶用药处理实验。将未施用过药的土壤的装入花盆中，加水待土壤完全湿润后，将靶标作物种子小麦和玉米种子播入盆内，植物在实验室条件下自然生长，每天对盆栽补水，待作物长至3-4叶期，进行11.25～22.5克/公顷剂 量的茎叶喷雾处理。通过室内安全性测定发现编号4的芳基尿嘧啶类化合物对玉米和小麦均有较好的安全性。
结果表明，本发明提供的芳基尿嘧啶类化合物对禾本科和阔叶草均具有较高的除草活性；而现有的苯嘧磺草胺对阔叶草具有除草活性，对禾本科杂草效果差；因此，本发明提供的芳基尿嘧啶类化合物的去除杂草范围宽，具有高效的除草活性。本发明提供的芳基尿嘧啶类化合物对难以防治的牛筋草等杂草有着更突出的除草活性。
另外，本发明提供表1所示的化合物进行茎叶处理是对牛筋草等恶性禾本科杂草和阔叶杂草有广谱的活性，所以作为茎叶处理可作为非选择性除草剂使用。例如，在土壤处理和茎叶处理时，化合物编号4的芳基尿嘧啶类化合物几乎对玉米和小麦无药害，并对禾本科和阔叶草才具有优秀的除草活性，可作为作物栽培的选择性除草剂用。
此外，化合物编号4和8的芳基尿嘧啶类化合物的溶解度25℃时约0.2克/升，大于对照化合物(2)的溶解度0.1克/升，其中化合物编号4的芳基尿嘧啶类化合物具有更好的水溶性和生物利用度，尤其对牛筋草除草活性高于对照化合物(2)。本发明的化合物结构(I)所示的化合物具有非常高的除草活性，可以使药剂用量大量减小，有助于减小环境污染问题。
以上所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，本领域普通技术人员可以理解实现上述实施例的全部或部分流程，并依本发明权利要求所作的等同变化，仍属于发明所涵盖的范围。

Claims (13)

  1. 一种如式Ⅰ所示的芳基尿嘧啶类化合物：
    Figure PCTCN2019098712-appb-100001
    其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤代烷基的碳原子数为1-4；
    X、Y独立地选自氢、卤素或氰基；
    Z选自氧原子或硫原子；
    其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；
    当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基。
  2. 如权利要求1所述的芳基尿嘧啶类化合物，其中，所述R 1和所述R 2中，所述烷基和所述卤代烷基的碳原子数为1-2。
  3. 如权利要求1所述的芳基尿嘧啶类化合物，其中，当所述Z为氧原子时，所述R 3为所述第一取代基团取代的C 1-C 4烷基、所述第一取代基团取代的C 2-C 4烯基或所述第一取代基团取代的C 2-C 4炔基。
  4. 如权利要求1所述的芳基尿嘧啶类化合物，其中，当所述Z为硫原子，所述R 3为所述第二取代基团取代的C 1-C 4烷基、所述第二取代基团取代的C 2-C 4 烯基或所述第二取代基团取代的C 2-C 4炔基。
  5. 如权利要求1所述的芳基尿嘧啶类化合物，其中，所述第一取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基；所述第二取代基团中的所述烷基氨基为碳原子数为1-3的烷基氨基，所述烷氧羰基为碳原子数为1-3的烷基羰基。
  6. 如权利要求1-5任意一项所述的芳基尿嘧啶类化合物，其中，所述R 1为三氟甲基，所述R 2为甲基或乙基；所述X、Y独立地选自氟或氯。
  7. 如权利要求6所述的芳基尿嘧啶类化合物，其中，当所述Z为氧原子，所述R 3选自至少被一个羟基、硝基或氨基取代的乙基；
    当所述Z为硫原子，所述R 3选自至少被一个羟基、硝基、氨基或甲氧羰基取代的乙基。
  8. 一种芳基尿嘧啶类化合物的制备方法，其中，包括以下步骤：
    (1)提供或制备如式Ⅱ所述的化合物A，以及提供或制备如式Ⅲ所述的化合物B，
    Figure PCTCN2019098712-appb-100002
    其中，R 1、R 2独立地选自氢、氨基、烷基或卤代烷基，所述烷基和所述卤代烷基的碳原子数为1-4；
    X、Y独立地选自氢、卤素或氰基；
    Z选自氧原子或硫原子；
    其中，当Z为氧原子，R 3为第一取代基团取代的C 1-C 8烷基、第一取代基团取代的C 2-C 8烯基或第一取代基团取代的C 2-C 8炔基；所述第一取代基团包括羟基、硝基、氨基或烷基氨基；
    当Z为硫原子，R 3为第二取代基团取代的C 1-C 8烷基、第二取代基团取代的C 2-C 8烯基或第二取代基团取代的C 2-C 8炔基；所述第二取代基团包括羟基、硝基、氨基、烷基氨基或烷氧羰基；
    (2)将所述化合物A和所述化合物B混合，然后添加催化剂进行反应，反应完毕后收集并纯化得到如式Ⅰ所示的芳基尿嘧啶类化合物，
    Figure PCTCN2019098712-appb-100003
  9. 一种农药组合物，其中，包括如权利要求1-7任意一项所述的芳基尿嘧啶类化合物或其农药学上可接受的盐。
  10. 如权利要求9所述的农药组合物，其中，所述农药组合物还包括农药学上可接受的配制佐剂；所述农药组合物可用于除草剂和/或落叶剂。
  11. 如权利要求9所述的农药组合物，其中，所述农药组合物可用于落叶剂时，所述芳基尿嘧啶类化合物的质量百分含量为0.1％-99.9％。
  12. 如权利要求9所述的农药组合物，其中，所述农药组合物还包括草甘膦或草铵膦。
  13. 如权利要求9所述的农药组合物，其中，所述农药组合物还包括农药学上可接受的配制佐剂；所述配制佐剂包括液体载体、固体载体、乳化剂、表面活性剂、粘合剂、增稠剂、着色剂、展开剂、防冻剂、防结块剂、崩解剂和抗分解剂中的一种或多种。
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