CN111961005B - Phenyl uracil compound and application thereof - Google Patents
Phenyl uracil compound and application thereof Download PDFInfo
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- CN111961005B CN111961005B CN202010731786.XA CN202010731786A CN111961005B CN 111961005 B CN111961005 B CN 111961005B CN 202010731786 A CN202010731786 A CN 202010731786A CN 111961005 B CN111961005 B CN 111961005B
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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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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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Abstract
The invention relates to a phenyl uracil compound and application thereof. Specifically, the invention provides a compound shown as a formula (I) or a salt of the compound shown as the formula (I), wherein R is1、R2、R3、R4And R5Each independently is hydrogen, C1‑6Alkyl radical, C2‑6Alkenyl radical, C2‑6Alkynyl, halo C1‑6Alkyl, halo C2‑6Alkenyl, halo C2‑6Alkynyl, C1‑6Alkoxy, etc.; r6Is hydrogen, cyano or C1‑6An alkyl group; x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1‑6Alkyl or halo C1‑6An alkyl group; r7And R8Each independently is hydrogen, C1‑6Alkyl or halo C1‑6An alkyl group. The compound has excellent herbicidal activity on barnyard grass, large crabgrass and purslane; has good safety to rice.
Description
Technical Field
The invention provides a novel phenyl uracil compound and a preparation method thereof; compositions containing these compounds and their use in agriculture.
Background
The application of chemical agents is a main method for preventing and controlling weeds, and a large amount of unreasonable herbicides are used for a long time, so that the preventing and controlling effect of the herbicides is obviously reduced, and meanwhile, resistant weeds are generated. Phenyl uracils are compounds with excellent biological activity, and the active ingredients still have some problems in use, such as: have no or only an inadequate herbicidal action on the weed plants, a too narrow spectrum of weed plants to be controlled or too low a selectivity in crops of useful plants.
Accordingly, there is a need to provide chemically active ingredients that can be advantageously used as herbicides.
Disclosure of Invention
The present invention provides a novel phenyluracil compound having an excellent herbicidal effect and an excellent selectivity between crops and weeds.
In one aspect, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof:
wherein:
R1、R2、R3、R4and R5Each independently is hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, halo C1-6Alkyl, halo C2-6Alkenyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C2-6Alkenyloxy, halogeno C2-6Alkenyloxy radical, C2-6Alkynyloxy, halo C2-6Alkynyloxy, C3-8Cycloalkyl or C3-8A cycloalkyloxy group;
R6is hydrogen, cyano or C1-6An alkyl group;
x, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-6Alkyl or halo C1-6An alkyl group;
R7and R8Each independently is hydrogen, C1-6Alkyl or halo C1-6An alkyl group.
In some of these embodiments, R1、R2、R3、R4And R5Each independently is hydrogen, halogen, cyano, hydroxy, nitro, amino, carboxyl, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, halo C1-4Alkyl, halo C2-4Alkenyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C2-4Alkenyloxy, halogeno C2-4Alkenyloxy radical, C2-4Alkynyloxy, halo C2-4Alkynyloxy, C3-6Cycloalkyl or C3-6A cycloalkyloxy group.
In some of these embodiments, R6Is hydrogen, cyano or C1-4An alkyl group.
In other embodiments, R6Is hydrogen or C1-3An alkyl group.
Preferably, R6Is hydrogen.
In some of these embodiments, X, Y is independently selected from the group consisting of hydrogen, halogen, nitro, amino, and amino, and amino, and amino, amino,Cyano radicals, C1-4Alkyl or halo C1-4An alkyl group.
In still other embodiments, X, Y is independently selected from hydrogen, halogen, nitro, amino, cyano, C1-3Alkyl or halo C1-3An alkyl group.
Preferably, X is fluorine; y is chlorine.
In some of these embodiments, R7And R8Each independently is hydrogen, C1-4Alkyl or halo C1-4An alkyl group.
In other embodiments, R7And R8Each independently is hydrogen, C1-3Alkyl or halo C1-3An alkyl group.
Preferably, R7And R8Each independently is methyl or trifluoromethyl.
In some of these embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, a nitroxide, or a salt thereof of a compound of formula (Ia):
wherein: r1、R2、R3、R4And R5Have the meaning as described in the present invention.
Preferably, R1、R2、R3、R4And R5Each independently is hydrogen, fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, propargyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy.
More preferably, R1、R2、R4And R5Each independently is hydrogen; r3Is methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
More preferablyEarth, R1、R2、R3And R4Each independently is hydrogen; r5Is methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy.
More preferably, the compound of the present invention is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
in another aspect, the present invention provides a composition comprising a compound of the invention, further optionally comprising an agriculturally acceptable adjuvant; such adjuvants include, but are not limited to, solvents, liquid diluents, solid diluents, emulsifiers, dispersants, defoamers, thickeners, binders, penetrants, preservatives, antifreeze, fillers, and the like.
In a further aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.
In a further aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a herbicide.
In particular, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling weeds such as barnyard grass, large crabgrass and purslane.
In a further aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a fungicide.
The indoor biological activity is measured by a microplate method, and the compound disclosed by the invention, such as the compound (1), has 90% of hypha growth inhibition activity on rhizoctonia solani at 0.1mg/L, and has a good inhibition effect.
The compound provided by the invention is a novel compound which is more effective to weeds and safe to crops.
The active compounds according to the invention can be used, for example, in the following plants: dicotyledonous weeds such as Abutilon, Amaranthus, Ambrosia, Monochoria, Chamomilla, atriplex, Bellis, Bidens, Capsella, Cardui Crispus, Cassia, cornflower, Chenopodium, Cirsium, Convolvulus, stramonium, Lysimachia, Glycine, Euphorbia, Galium, Echinacea, Amurella, Hypericum, Hibiscus, Ipomoea, Diospermum, Cruciferae, Monogyne, Matricaria, Mentha, Lodigris, forgetfulia, Papaver, Pharbita, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Phaseolus, Podocarpus, Thalictrum, Caraway, Senecio, Stephania, Selaginella, Sesbania, Sida, Solanum, Picrasma, Cichorium, Saint, chicory, Potentilla, and herba Siphonostegiae, xanthium species.
Dicotyledonous crop genera such as genus peanut, genus beet, genus Brassica, genus Cucumis, genus Cucurbita, genus Helianthus, genus Daucus, genus Glycine, genus gossypium, genus Ipomoea, genus Lactuca, genus Linum, genus Lycopersicon, genus Nicotiana, genus Phaseolus, genus Pisum, genus Solanum, genus Neisseria.
Monocotyledonous weeds such as aegilops, agropyron, bentgrass, alopecurus, pseudobentgrass, avena, brachiaria, bromus, tribulus, dayflower, bermudagrass, sedge, cogongrass, digitaria, barnyard, eleocharis, cricket, teff, fescue, orchis, fimbria, imperata, cockere, mollissima, moleplant, pennisetum, toxylum, monochamus, panicum, broomrape, grass, echevergrass, parva, pinus, arrowhead, charpy, setaria, sorghum.
Monocotyledonous crop genera such as Allium, Coprinus, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, sorghum, triticale, Triticum, Zea.
The active compounds of the invention can also be prepared in conventional formulations for practical use. Examples of the formulation include solutions, wettable powders, emulsions, emulsifiable concentrates, suspensions, dusts, water dispersible granules, tablets, granules, microcapsules, and the like. These formulations may be prepared by methods conventional in the art. For example, the active compound may be mixed with agriculturally acceptable adjuvants, including, but not limited to, solvents, liquid diluents, solid diluents, emulsifiers, dispersants, defoamers, thickeners, binders, penetrants, preservatives, antifreeze, fillers, and the like.
When used, the commercially available formulations are diluted in the usual manner, if desired, for example in wettable powders, concentrated emulsions, suspensions and granules suspended in water, using water. Powders, granules for soil application or solutions for spreading and spraying generally do not require further dilution with inert substances before use. The amount of active compound required to be used varies with the external conditions, such as temperature, humidity, nature of the herbicide used, etc. It may vary widely, for example between 0.001 and 1.0kg/ha, or more of active substance, but preferably between 0.005 and 750g/ha, in particular between 0.005 and 250 g/ha.
On the basis of these formulations, it is also possible to mix them with other insecticide active substances, such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or plant growth regulators, either premixed or mixed in containers.
Detailed Description
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used were commercially available unless otherwise specified.
Examples
Intermediate A5- (4-methoxyphenoxy) -2-nitrobenzenesulfonamide
To a solution of p-methoxyphenol (0.15mol) in N, N-dimethylacetamide (50mL) was added potassium hydroxide (0.1mol), and the mixture was heated to 120 ℃ to dissolve the potassium hydroxide, and then benzyl (5-chloro-2-nitrophenyl) sulfane (0.15mol) was added, followed by heating at 155 ℃ under stirring for 6 hours and cooling. Water (30mL) was added, the organic phase was extracted with benzene (50mL), the extract was washed with aqueous sodium hydroxide (0.05M,30mL) and water (30mL), dried over anhydrous sodium sulfate, and the benzene was distilled off. The residue was recrystallized from ethanol to give benzyl (5- (4-methoxyphenoxy) -2-nitrophenyl) sulfane as a yellow solid.
A mixture of benzyl (5- (4-methoxyphenoxy) -2-nitrophenyl) sulfane (0.01mol) in glacial acetic acid (200mL) and water (30mL) was purged with chlorine gas at 10 ℃ under stirring, and then allowed to stand at room temperature overnight. The mixture was poured into water (100mL), the organic phase was extracted with benzene (100mL), and the extract was washed with water (50mL) and dried over anhydrous sodium sulfate to give 5- (4-methoxyphenoxy) -2-nitrobenzene-1-sulfonyl chloride as a red oil.
5- (4-methoxyphenoxy) -2-nitrobenzene-1-sulfonyl chloride (0.008mol) was dissolved in ethyl acetate (50mL), and the resulting solution was dropwise added to ammonia-saturated ethyl acetate, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and was washed with water (30mL) and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was recrystallized from ethanol to give 1.72g of 5- (4-methoxyphenoxy) -2-nitrobenzenesulfonamide in 66.3% yield.
MS-ESI:m/z 325.1[M+H]+.
Referring to the preparation of intermediate a, the intermediates of table 1 were prepared.
Table 1 intermediate structures and characterization data
Example 12-chloro-4-fluoro-N- ((5- (4-methoxyphenoxy) -2-nitrophenyl) sulfonyl) -5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzamide
Slowly dropwise adding a dichloromethane (25mL) solution of 2-chloro-4-fluoro-5- (3-methyl-2, 6-dioxo-4- (trifluoromethyl) -2, 3-dihydropyrimidin-1 (6H) -yl) benzoyl chloride (0.005mol) into a dichloromethane (25mL) solution of 5- (4-methoxyphenoxy) -2-nitrobenzenesulfonamide (0.005mol) at 0 ℃, adding triethylamine (0.52g), and reacting at room temperature for 4H after dropwise adding; after the reaction was completed, the reaction mixture was washed with hydrochloric acid (2M) 3 times, then with water 3 times, and the organic phase was washed with water to neutrality and then dried with anhydrous sodium sulfate to obtain 2.79g of a white solid powder with a yield of 83%.
MS-ESI:m/z 673.0[M+H]+.
1H NMR(500MHz,CDCl3)δ8.38(s,1H),8.19(s,1H),7.97(d,J＝5.0Hz,2H),7.92(s,1H),7.56(s,1H),7.30-7.06(s,4H),6.26(s,1H),4.01(s,3H),3.79(s,3H).
Referring to the preparation method of example 1, the objective compounds of table 2 were prepared.
TABLE 2 Structure and characterization data for the target Compounds
Herbicidal Activity test
Planting barnyard grass, crab grass and purslane respectively by a pot culture method, covering soil about 1.0cm, and carrying out spray treatment when seedlings grow to 2-4 leaves. Before the compound is sprayed, a proper amount of DMF is used for dissolving, and then distilled water containing 1 per mill of Tween-80 emulsifier is used for diluting. After the application according to the set dosage, the mixture is moved to the outdoor for culture, and the activity (%) of the weeds is checked 21 days later; where 0 indicates no harm or normal growth process and 100 indicates complete death of at least the aerial part.
The activity test of the invention shows that the comparative compound is saflufenacil, the structural formula of the saflufenacil is as follows, and the test results are shown in table 3:
TABLE 3 controlling effect of the compounds of the invention on weeds
As can be seen from Table 3, the compounds of the present invention have excellent herbicidal activity against barnyard grass, crab grass and purslane; especially has better control effect on barnyard grass and crabgrass than the prior art compounds of the same type.
Crop safety testing
The method comprises the steps of sowing rice by a pot culture method, covering soil about 1.0cm, and carrying out spray treatment when seedlings grow to 2-4 leaves. Before the compound is sprayed, a proper amount of DMF is used for dissolving, and then distilled water containing 1 per mill of Tween-80 emulsifier is used for diluting. After the pesticide is applied according to the set dose, the mixture is moved to the outdoor for culture, and the safety of the mixture to the rice is investigated after 21 days; where 0 means no damage or normal growth process and 100 means no emergence or at least complete death of the aerial parts.
Examples 1, 4, 5 and 6 of the present invention showed good safety to rice, for example, example 1 showed 0 inhibition to rice at 75g/ha, indicating that the compound of example 1 has good safety to rice.
Claims (7)
1. A compound of formula (Ia) or a salt thereof:
wherein:
R1and R5Each independently is hydrogen, C1-4Alkoxy radical, C2-4Alkenyloxy or C3-6A cycloalkyloxy group;
R2and R4Each independently is hydrogen;
R3is hydrogen or C1-4An alkoxy group.
2. The compound of claim 1, wherein
R1And R5Each independently is hydrogen, methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy;
R2and R4Each independently is hydrogen;
R3is hydrogen, methoxy, ethoxy, n-propoxy or isopropoxy.
3. The compound of claim 2, wherein
R1、R2、R4And R5Each independently is hydrogen;
R3is methoxy, ethoxy, n-propoxy or isopropoxy.
4. The compound of claim 2, wherein
R1、R2、R3And R4Each independently is hydrogen;
R5is methoxy, ethoxy, n-propoxy, isopropoxy, allyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy or cyclohexyloxy.
5. The compound of claim 1, which is a compound having one of the following structures or a salt of a compound having one of the following structures:
6. a composition comprising a compound of any one of claims 1-5; further optionally comprising an agriculturally pharmaceutically acceptable adjuvant.
7. Use of a compound according to any one of claims 1 to 5 or a composition according to claim 6 as a herbicide.
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| CN202010731786.XA CN111961005B (en) | 2020-07-27 | 2020-07-27 | Phenyl uracil compound and application thereof |
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| CN202010731786.XA CN111961005B (en) | 2020-07-27 | 2020-07-27 | Phenyl uracil compound and application thereof |
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| CN111961005B true CN111961005B (en) | 2022-04-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9112566D0 (en) * | 1991-06-11 | 1991-07-31 | Shell Int Research | Sulphonamide herbicides |
| WO2004089914A1 (en) * | 2003-04-08 | 2004-10-21 | Basf Aktiengesellschaft | Benzenesulphonamide derivatives as herbicides or desiccant/defoliant compounds |
| CN109232442B (en) * | 2018-09-13 | 2021-11-02 | 深圳大学 | Aryl uracil compound or agriculturally and pharmaceutically acceptable salt thereof, preparation method thereof and herbicide composition |
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