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CN-122010866-A - Robine derivative and its synthesis method and application

CN122010866ACN 122010866 ACN122010866 ACN 122010866ACN-122010866-A

Abstract

The application relates to the field of chemical synthesis, in particular to a rhodanine derivative, a synthesis method and application thereof. The application prepares the rhodanine derivative and applies the rhodanine derivative to agricultural and forest source disease fungi, and compared with the prior art, the derivative synthesized by the application has quite good inhibition effect on aschersonia aurantiaca, has a certain inhibition effect on rhizoctonia solani, rice blast germ, conidium pineri and fusarium oxysporum, and provides a new direction for preventing and controlling plant source diseases.

Inventors

  • Di Sikai
  • PENG JINSONG
  • CHEN CHUNXIA
  • LV XIAODI
  • ZHAO ZIXIANG
  • Zhang Junrou
  • LIU HUAJIN
  • HOU MO

Assignees

  • 东北林业大学

Dates

Publication Date
20260512
Application Date
20251219

Claims (10)

  1. 1. The rhodanine derivative for inhibiting or killing plant pathogenic fungi is characterized by having a structure shown as a general formula (I) or a general formula (II): ; Wherein, in the general formula (I): R 1 is selected from one of hydrogen, methyl and n-butyl; R 2 is selected from one of phenyl, 4- (dimethylamino) phenyl, (E) -styryl, 2-hydroxynaphthalen-1-yl, 3, 4-dimethoxyphenyl, 4-methoxyphenyl, 3, 4-dimethylphenyl, 3, 5-dimethoxyphenyl, 4-chlorophenyl, 4-nitrophenyl, 2-methoxyphenyl, 1H-pyrrol-2-yl, naphthalen-2-yl, 3-bromo-5-chlorophenyl, (E) -2, 6-dimethylhept-5-enyl, 6-bromo-2-hydroxynaphthalen-1-yl, 6-fluoro-3-nitronaphthalen-2-yl, 2, 4-difluoro-3-nitronaphthalen-1-yl, 3-cyanophenyl, 4- (tert-butyl) phenyl, 4- (trifluoromethyl) phenyl, 5-bromothiophen-2-yl, benzo [ d ] thiazol-2-yl, benzo [ b ] thiophen-2-yl, benzofuran-2-yl; In formula (II): r 1 is selected from one of hydrogen and methyl; R 2 is selected from one of phenyl, (E) -2-phenylvinyl, 5-bromothiophen-2-yl, benzo [ b ] thiophen-2-yl, 4- (trifluoromethyl) phenyl, 3, 4-dimethoxyphenyl and 2-methoxyphenyl.
  2. 2. A process for the preparation of a rhodanine derivative for inhibiting or killing phytopathogenic fungi according to claim 1, comprising the following steps: (1) Mixing L-alanine or glycine, carbon disulfide and ammonia water for nucleophilic addition reaction, and recrystallizing and purifying a reaction product to obtain an intermediate 1; (2) Nucleophilic substitution reaction is carried out on the intermediate 1 and chloroacetic acid under alkaline condition, then cyclization is carried out under acidic condition, and intermediate 2 is obtained through crystallization; (3) And (3) dissolving the intermediate 2 and an aldehyde compound in an organic solvent, carrying out addition-elimination reaction in the presence of an alkaline catalyst, and carrying out post-treatment after the reaction is finished to obtain the rhodamine derivative.
  3. 3. The preparation method of the catalyst is characterized in that the molar ratio of the L-alanine or glycine to the carbon disulfide to the ammonia water added in the step (1) is 1:1:3-4, the molar ratio of the intermediate 1 to the chloroacetic acid added in the step (2) is 1:1-1.2, and the molar ratio of the intermediate 2 to the aldehyde compound added in the step (3) is 1:1.
  4. 4. The preparation method according to claim 2, wherein the solvent for the reaction in the step (1) is water, the reaction is carried out under ice bath conditions for 0.5 to 1 hour, and the solvent for the recrystallization is ethanol.
  5. 5. The preparation method according to claim 2, wherein the alkaline condition in the step (2) is adding sodium bicarbonate, the reaction temperature is 25 ℃, the reaction time is 1 hour, the acidic condition is adding concentrated hydrochloric acid, the reaction time is 12 hours, and the crystallization process is carried out at 0 ℃.
  6. 6. The preparation method according to claim 2, wherein the aldehyde compound in the step (3) is selected from aromatic aldehyde or alkyl aldehyde, the organic solvent is ethanol, the alkaline catalyst is ammonia water, the reaction temperature is 60 ℃, and the reaction time is 1 hour.
  7. 7. The preparation method according to claim 2, characterized in that: The post-treatment step of the step (3) comprises the steps of filtering the reaction liquid to remove the precipitate, adding water and methylene dichloride into the filtrate, adjusting the pH value to 2-3, heating and rotationally evaporating to obtain solid, and filtering to obtain the product.
  8. 8. A rhodanine derivative for inhibiting or killing phytopathogenic fungi, prepared by the method of any one of claims 2-7.
  9. 9. Use of a rhodanine derivative according to claim 1 or 8 for inhibiting or killing plant pathogenic fungi in the preparation of a formulation for inhibiting or killing plant pathogenic fungi.
  10. 10. The method according to claim 9, wherein the plant pathogenic fungi comprise any one or more of Rhizoctonia solani, pyricularia oryzae, mortierella aurantiaca, mortierella pinicola or Fusarium oxysporum.

Description

Robine derivative and its synthesis method and application Technical Field The invention relates to the field of chemical synthesis, in particular to a rhodanine derivative, a synthesis method and application thereof. Background Grain and ecological safety are important basic stones for national safety, and concern for national folk life and social stability. The diseases caused by plant pathogenic fungi not only seriously threaten the stable and high yield of grain crops such as rice, but also form a serious challenge for preventing and controlling serious tree diseases such as poplar rotten skin disease (caused by aschersonia aleyrodis), pine needle rot (caused by aschersonia Pini), and the like. For example, rhizoctonia solani-induced root rot and damping off can lead to crop yield reductions of 25% to 100%, severely limiting agricultural sustainable development. Although the use of chemical fungicides has controlled disease spread to some extent, agents that rely on a single mechanism of action for a long period of time have forced pathogenic bacteria to evolve complex resistance mechanisms, resulting in significant attenuation of the control efficacy of traditional fungicides. In addition, the problem of decay and mycotoxin pollution caused by fungi after agricultural product is picked also constitutes a potential threat to food safety. Therefore, the development of novel plant fungus inhibitors which have broad-spectrum antibacterial activity, are environment-friendly and can overcome the existing drug resistance has become an urgent need for ensuring the safe production of agriculture and forestry. The rhodanine derivative has been proved to have remarkable pharmacological effects in the fields of antibiosis, antivirus, antitumor and the like due to the thiazole ring, the arylmethylene and the thio groups which are characteristic in the structure. However, research on the development and application of rhodanine and its derivatives in the field of agricultural chemistry, especially as plant pathogenic fungi inhibitors, is still in a starting stage, and the potential agricultural application value of rhodanine and its derivatives has not been fully exploited. In view of the above, the invention adopts a high-efficiency drug molecular design strategy based on the dominant framework structure of the rhodanine, and synthesizes a series of novel rhodanine derivatives through structural modification. The invention aims to explore the potential of the compound in controlling main agricultural and forestry pathogenic bacteria such as rhizoctonia solani, rice blast bacteria, aschersonia aurantiaca and the like, and screens out high-activity candidate molecules through structure-activity relation research so as to break through the resistance barrier of the traditional bactericide and provide an innovative solution with high efficiency and low toxicity for green prevention and control of agricultural and forestry crop fungal diseases. Disclosure of Invention In order to achieve the above object, a first technical scheme of the present application discloses a rhodanine derivative, which has a structure as shown in general formula (I) or general formula (II): Wherein, in the general formula (I): R 1 is selected from one of hydrogen, methyl and n-butyl; R 2 is selected from one of phenyl, 4- (dimethylamino) phenyl, (E) -styryl, 2-hydroxynaphthalen-1-yl, 3, 4-dimethoxyphenyl, 4-methoxyphenyl, 3, 4-dimethylphenyl, 3, 5-dimethoxyphenyl, 4-chlorophenyl, 4-nitrophenyl, 2-methoxyphenyl, 1H-pyrrol-2-yl, naphthalen-2-yl, 3-bromo-5-chlorophenyl, (E) -2, 6-dimethylhept-5-enyl, 6-bromo-2-hydroxynaphthalen-1-yl, 6-fluoro-3-nitronaphthalen-2-yl, 2, 4-difluoro-3-nitronaphthalen-1-yl, 3-cyanophenyl, 4- (tert-butyl) phenyl, 4- (trifluoromethyl) phenyl, 5-bromothiophen-2-yl, benzo [ d ] thiazol-2-yl, benzo [ b ] thiophen-2-yl, benzofuran-2-yl; In formula (II): r 1 is selected from one of hydrogen and methyl; R 2 is selected from one of phenyl, (E) -2-phenylvinyl, 5-bromothiophen-2-yl, benzo [ b ] thiophen-2-yl, 4- (trifluoromethyl) phenyl, 3, 4-dimethoxyphenyl and 2-methoxyphenyl. The second technical scheme of the application discloses a preparation method of the rhodanine derivative, which comprises the following steps: (1) Mixing L-alanine or glycine, carbon disulfide and ammonia water for nucleophilic addition reaction, and recrystallizing and purifying a reaction product to obtain an intermediate 1; (2) Nucleophilic substitution reaction is carried out on the intermediate 1 and chloroacetic acid under alkaline condition, then cyclization is carried out under acidic condition, and intermediate 2 is obtained through crystallization; (3) And (3) dissolving the intermediate 2 and an aldehyde compound in an organic solvent, carrying out addition-elimination reaction in the presence of an alkaline catalyst, and carrying out post-treatment after the reaction is finished to obtain the rhodamine derivative. Further, the molar ratio o