CN-119100996-B - Pyrimidine-biaryl compound, preparation method and application as herbicide

Abstract

The invention relates to herbicide technology, and aims to provide a pyrimidine-biaryl compound, a preparation method and application as herbicide. The pyrimidine-biaryl compound has the structural formula shown in the general formula (I), and the application method of the compound is to apply a herbicidal activity amount of the compound to the leaves of pre-emergent or post-emergent weeds. Compared with the prior art, the compound can be used as a post-emergence herbicide and a pre-emergence herbicide, has a broad herbicide controlling spectrum and has a wider application window period.

Inventors

• WU JUN
• YAN YITAO
• GU HAINING

Assignees

• 浙江大学

Dates

Publication Date

20260508

Application Date

20240306

Claims (8)

1. 1. The pyrimidine-biaryl compound is characterized in that the structural formula of the compound is shown as a general formula (I): ; In the formula (I), ar is selected from any one of Ar 1-Ar 30 shown in the following: ; ; ; ; ; ; ; ; Wherein, the R 1 is hydrogen, halogen, amino, hydroxy, cyano, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or C 1 -C 2 alkyl; r 2 is hydrogen, halogen, amino, methoxy or C 1 -C 2 alkyl; R 3 is hydrogen, halogen, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, acetyl, benzoyl, carboxyl or methyl ester; R 4 is hydrogen, halogen, methoxy or C 1 -C 2 alkyl; r 5 is hydrogen or fluorine.
2. 2. The pyrimidine-biaryl compound of claim 1, wherein the halogen is fluorine, chlorine or bromine.
3. 3. The process for the preparation of pyrimidine-biaryl compounds according to claim 1, wherein the preparation of the compounds is effected by the following scheme one or scheme two: the synthesis route I is as follows: ; In the formula (B), LG 1 represents a boron-containing substituent; The synthesis route II is as follows: ; In the formula (C), LG 2 represents a boron-containing substituent, and in the formula (D), X 2 represents a leaving group.
4. 4. A method according to claim 3, characterized in that the preparation method based on the first synthetic route comprises in particular: Adding an intermediate shown in a formula (A), a compound shown in a formula (B), potassium carbonate and a palladium catalyst into a proper amount of solvent according to a molar ratio of 1.3 to 6 to 0.05, reacting for 1 hour at 100 ℃, and separating and purifying a reaction product through silica gel column chromatography to finally obtain the pyrimidine-biaryl compound shown in the formula (I).
5. 5. A method according to claim 3, characterized in that the preparation method based on synthetic route two comprises in particular: (1) Adding a compound shown in a formula (C), a compound shown in a formula (D), sodium carbonate and a palladium catalyst into a proper amount of solvent according to a molar ratio of 1.1.3.5.0.05, and reacting for 1 hour at 100 ℃ to obtain a compound shown in a formula (E); (2) Taking a compound shown in a formula (E), salicylaldehyde and sodium borohydride according to a molar ratio of 1.1.5 to 1.5, adding the compound shown in the formula (E) and salicylaldehyde into methanol to react for 0.5 hour at room temperature, then adding sodium borohydride, and continuing to react for 0.5 hour at room temperature to obtain the compound shown in the formula (F); (3) Adding a compound shown in a formula (F), equivalent 2-methylsulfonyl-4, 6-dimethoxy pyrimidine and cesium carbonate into a proper amount of 1, 4-dioxane according to a molar ratio of 1.1.2.1.5, reacting for 4 hours at 110 ℃, and separating and purifying a reaction product through silica gel column chromatography to finally obtain the pyrimidine-biaryl compound shown in the formula (I).
6. 6. A herbicidal composition comprising a herbicidally active amount of a pyrimidine-biaryl compound of claim 1 and at least one formulation adjuvant.
7. 7. A process for preparing a herbicidally active composition, characterized in that a herbicidally active amount of a pyrimidine-biaryl compound of claim 1 is mixed with at least one formulation auxiliary.
8. 8. The method for using pyrimidine-biaryl compounds as agrochemical herbicides according to claim 1, wherein the herbicidally active amount of pyrimidine-biaryl compounds acts on leaves of pre-or post-emergent weeds, which are any one of barnyard grass and crabgrass.

Description

Pyrimidine-biaryl compound, preparation method and application as herbicide Technical Field The invention relates to a novel pyrimidine-biaryl compound, in particular to a pyrimidine-biaryl compound, a preparation method and application of the pyrimidine-biaryl compound as herbicide. Background In the process of grain planting, the herbicide is used for improving the yield per unit area and the quality of crops. On the other hand, however, the use of herbicides also has a negative environmental impact, such as increased weed resistance, which increases the amount of herbicide used, thus placing a great risk to the ecosystem. Therefore, the development of efficient, low-toxicity, easily degradable, environmentally friendly herbicides has become an important development direction for innovative research. Pyrimidine salicylic acid herbicides are widely used for weed control in paddy fields and cotton fields, and up to now, 5 herbicides have been registered in related countries and used for control of important weeds in farmlands, and the structural formulas thereof are respectively: As a result of the widespread use of these herbicides, increased weed resistance results and threatens the continued use of these herbicides. Previous studies have shown that the target of pyrimidine salicylic herbicides is acetoacetate synthase (AHAS), and that the mechanism of weed resistance to these herbicides is mainly manifested in two aspects, target site mutation and metabolic resistance in non-target resistance (increased metabolic capacity for herbicides). Therefore, designing an anti-resistance inhibitor would be a significant challenge. To overcome this difficulty, it was found that a class of pyrimidine-biphenyl compounds, which have been discovered based on structural optimization of pyrimidine salicylic herbicides, retaining the pyrimidine skeleton and carboxylic acid groups, with phenyl or heteroaryl groups introduced at the 6-position of the benzene ring, were effective against AHAS-resistant weeds, tarragon (Descurania Sophia) and amaranthus auriculatus (AMMANNIA ARENARIA) which are resistant to AHAS inhibitors. Biaryl compounds are basic skeletons of natural products, are common molecular substructure in pharmaceutical chemistry, can adapt to various drug targets due to the flexibility of internal rotation, are important components in the molecular structure of pesticides, and are also important skeletons in the material science, so that molecules containing the knot skeletons have wide application prospects. And secondly, the compound can be quickly constructed by using Suzuki-Miyaura Cross-Coupling reaction (Suzuki-Miyaura Cross-Coupling), so that a new chemical space can be effectively expanded. Pyrimidine salicylic herbicides each contain a pyrimidine skeleton and a carboxyl group or an ester thereof, and previous studies have thought that both substructures are required to be retained in the design of the inhibitor to maintain herbicidal activity. Thus, the research direction of the man skilled in the art is always around this idea to develop new herbicides, which results in a continuous push to products with newer chemical structures and better resistance properties. Therefore, the development of such novel pyrimidine-biaryl compounds for weed control is urgent and of great significance. Disclosure of Invention The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a pyrimidine-biaryl compound, a preparation method and application as herbicide. The compound can be used as an agrochemical herbicide for weed control in the agricultural field, and shows excellent herbicidal activity after and before emergence. In order to solve the technical problems, the invention adopts the following solutions: Provided is a pyrimidine-biaryl compound, the structural formula of which is shown in the general formula (I): In the formula (I), ar is selected from any one of Ar 1-Ar 30 shown in the following: Wherein, the R 1 is hydrogen, halogen, amino, hydroxy, cyano, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl or C 1-C2 alkyl; r 2 is hydrogen, halogen, amino, methoxy or C 1-C2 alkyl; R 3 is hydrogen, halogen, C 1-C2 alkyl, C 1-C2 alkoxy, acetyl, benzoyl, carboxyl or methyl ester; R 4 is hydrogen, halogen, methoxy or C 1-C2 alkyl; r 5 is hydrogen or fluorine. As a preferred embodiment of the present invention, the halogen is fluorine, chlorine or bromine, the C 1-C2 alkyl is methyl (Me, CH 3) or ethyl (Et, C 2H5);C1-C2 alkoxy is methoxy (MeO, CH 3 O) or ethoxy (EtO, C 2H5 O). The pyrimidine-biaryl compounds of the present invention may be shown as specific compounds I-1~I-78 in combination with the specific structures of 78 Ar shown in formula (I) and Table 1, but the present invention is not limited to these compounds. TABLE 1 The invention further provides a preparation method of the pyrimidine-biaryl compound, which is realized through the following