CN-119100995-B - Acetohydroxyacid synthase inhibitors, process for their preparation and their use as herbicides

Abstract

The invention relates to an inhibitor compound, and aims to provide an acetohydroxy acid synthetase inhibitor, a preparation method thereof and application thereof as herbicide. The structural formula of the compound is shown as a formula (I), and the compound specifically inhibits the activity of acetohydroxy acid synthetase or a mutant W574L thereof in plants. The invention further provides a method for using the compound as an agrochemical herbicide. The compound has good enzyme inhibition activity on wild acetohydroxyacid synthase and/or mutant W574L thereof, can be used as an agrochemical herbicide for preventing and controlling various weeds in the agricultural field, can be used as a pre-emergence herbicide and a post-emergence herbicide, has special effects on preventing and controlling malignant weed euphorbia lathyris, and has the characteristics of low dosage, excellent herbicidal activity, wide herbicidal spectrum, good conductivity, wide use window period, safety to rice and the like.

Inventors

• WU JUN
• CHEN YINGLU
• GU HAINING

Assignees

• 浙江大学

Dates

Publication Date

20260508

Application Date

20240306

Claims (8)

1. 1. An acetohydroxyacid synthase inhibitor for use as an agrochemical herbicide to control resistant euphorbia lathyris, characterized in that said inhibitor is a compound represented by the formula (I): ; The compound specifically inhibits the activity of acetohydroxy acid synthetase or its mutant W574L in plants.
2. 2. The method for preparing acetohydroxy acid synthetase inhibitor according to claim 1, wherein the synthetic route of the preparation method is shown as the following formula: 。
3. 3. The method according to claim 2, characterized in that it comprises in particular the following steps: (1) Methanol or ethanol is used as a solvent of a reaction system, and 4- (4-chlorophenoxy) aniline and salicylaldehyde are reacted to prepare corresponding Schiff base, wherein the molar ratio of the 4- (4-chlorophenoxy) aniline to the salicylaldehyde is controlled to be 1:1.2, the reaction temperature is room temperature, and the reaction time is 2 hours; (2) Sodium borohydride or potassium borohydride is used as a reducing agent, methanol or ethanol is used as a solvent of a reaction system, and a benzyl amine compound is prepared by reducing Schiff base, wherein the molar ratio of the Schiff base to the reducing agent is controlled to be 1:1.5, the reaction temperature is room temperature, and the reaction time is 0.5 hour; (3) The target product acetohydroxyacid synthase inhibitor is prepared by the reaction of a benzylamine compound and 2-methylsulfonyl-4, 6-dimethoxy pyrimidine, potassium carbonate or cesium carbonate is used as alkali in the reaction, 1, 4-dioxane is used as a reaction solvent, the molar ratio of the benzylamine compound, the 2-methylsulfonyl-4, 6-dimethoxy pyrimidine and the alkali is controlled to be 1:1.2:1.2, the reaction temperature is the boiling point of the solvent, the reaction time is 1 hour, and the purification of the finally obtained target product is realized by silica gel chromatography or recrystallization.
4. 4. A herbicidal composition comprising a herbicidally active amount of an acetohydroxyacid synthase inhibitor according to claim 1 and at least one formulation auxiliary.
5. 5. A process for preparing a herbicidally active composition, characterized in that a herbicidally active amount of an acetohydroxyacid synthase inhibitor according to claim 1 and at least one formulation auxiliary are mixed.
6. 6. Use of an acetohydroxyacid synthase inhibitor according to claim 1 as an agrochemical herbicide, characterized in that the compound specifically inhibits the activity of p-acetohydroxyacid synthase or a mutant W574L thereof in a plant body.
7. 7. The method for using an acetohydroxy acid synthetase inhibitor as an agrochemical herbicide for controlling resistant euphorbia lathyris, according to claim 1, characterized in that a herbicidally active amount of the acetohydroxy acid synthetase inhibitor is applied to leaves of resistant euphorbia lathyris in the pre-or post-emergence period, which specifically inhibits the activity of acetohydroxy acid synthetase or a mutant W574L thereof in the resistant euphorbia lathyris plant.
8. 8. The method of using the acetohydroxy acid synthetase inhibitor as an agrochemical herbicide having a broad herbicidal activity as claimed in claim 1, wherein a herbicidally active amount of the acetohydroxy acid synthetase inhibitor is allowed to act on the leaves of weeds, the compound specifically inhibiting the activity of p-acetohydroxy acid synthetase or a mutant thereof W574L in the weed plant; The weeds are any one of semen Euphorbiae, barnyard grass, crab grass, amaranth, herba Eleusines Indicae, green bristlegrass, poa pratensis, fructus Chenopodii, herba Portulacae, herba Setariae viridis, herba Inulae, mustard, heterotypic Cyperus, and rhizoma Cyperi.

Description

Acetohydroxyacid synthase inhibitors, process for their preparation and their use as herbicides Technical Field The invention relates to an inhibitor compound, in particular to an acetohydroxy acid synthetase inhibitor, a preparation method thereof and application thereof as herbicide. The target of the compound is acetohydroxy acid synthetase or mutant W574L thereof, and the compound can be used as herbicide for weed control in the agricultural field. The product has special effect on preventing and treating malignant weed Euphorbia lathyris, and is superior to common commercial herbicides cyhalofop-butyl and penoxsulam in preventing and treating resistance Euphorbia lathyris. Background Semen Euphorbiae [ Leptochloa chinensis (L.) Nees ] belongs to grassy weeds, and is a malignant weed worldwide. The seed quantity of the euphorbia lathyris is extremely large (45000 seeds can be formed in each plant on average), the tillering capacity is extremely high (the tillering number can be up to 48.2), and the characteristic that the euphorbia lathyris is thousands of Jin Zihan are wet-loving is added, so that the euphorbia lathyris is extremely suitable for the euphorbia lathyris to occur and to be rapidly diffused in a paddy field, and evolves into a main weed population in the paddy field, and the main weed population competes with paddy to be harmful, so that the paddy is seriously reduced in yield. With the popularization and development of paddy field direct seeding technology and no-tillage technology, the damage of the semen Euphorbiae is increasingly serious. Studies show that when the density of the stephania cepharantha reaches 21 plants/m 2, the yield of the rice can be reduced by 44.36 percent. In the prevention and control of the semen euphorbiae, the semen euphorbiae and the rice are basically synchronous to emerge, so that the prevention and control are difficult to realize through time difference. In chemical control, the herbicide selection for the semen Euphorbiae is less. At present, the farmland weed control mainly uses aryloxy-phenoxy propionate (aryloxyphenoxypropionate, APP) herbicides such as cyhalofop-butyl, fenoxaprop-p-ethyl, metamifop and the like. Such herbicides are acetyl-coenzyme A carboxylase (ACCase) inhibitors and can only be used for post-emergence control of euphorbia lathyris. Cyhalofop-butyl is most widely used in paddy fields, but long-term overfrequent use of the same type of herbicide also leads to rapid occurrence of resistant semen euphorbiae, and the resistance coefficient of a semen euphorbiae population which is partially resistant to cyhalofop-butyl to the herbicide reaches 191.6 times. In addition, in southeast asia, china and the like, it has been found that stephania sinica diels, which are resistant to ACCase inhibitor herbicides, are also cross-resistant to inhibitors of other action targets, such as propanil (photosystem II inhibitor herbicide) and quinclorac (growth hormone herbicide). Mechanisms by which resistance occurs in Euphorbia lathyris include target resistance and non-target resistance. The reported target resistance of the semen euphorbiae is mainly from amino acid mutations at 1781 site, 1999 site and 2027 site, and the generation of non-target resistance is possibly related to the enhancement of glutathione S-transferase (GSTs) activity, and the enhancement of GSTs activity can improve the metabolic decomposition rate of weeds to herbicides, so that the semen euphorbiae can generate drug resistance. Acetohydroxy acid synthase (acetohydroxyacid synthase, AHAS) is a key enzyme that catalyzes the first stage of the branched-chain amino acid-leucine, valine and isoleucine biosynthetic pathway. Acetohydroxy acid synthetases may catalyze two molecules of pyruvic acid to produce alpha-acetolactic acid, or one molecule of pyruvic acid and alpha-butanoic acid to produce 2-acetyl-2-hydroxybutyric acid. Acetohydroxy acid synthetase inhibitors inhibit the catalytic activity of AHAS in plants, so that synthesis of branched chain amino acids is blocked, synthesis of proteins is influenced, cell division is further inhibited, and accordingly plant tissues are prevented from being green, yellowing and plant growth are inhibited, and finally plant death is caused. In addition, the hydroxy acid synthetase exists only in plants, fungi and bacteria, and does not exist in animals, so that the inhibitor designed by taking the hydroxy acid synthetase as a target has extremely high biological safety for mammals. Meanwhile, the herbicide has low application dosage, broad-spectrum herbicidal activity and high safety to crops, and is the most important herbicide variety at present. However, existing commercial herbicides targeting acetohydroxyacid synthetases, due to the specificity of their compound backbone structure, are not effective in controlling resistant euphorbia lathyris when used at the recommended doses in the field. Furthermore, AHAS-targeted herbicides do not