CN-122011023-A - Tetrahydrogeranyl quaternary phosphonium salt compound and preparation method and application thereof

Abstract

The invention relates to a tetrahydrogeranyl quaternary phosphonium salt compound, a preparation method thereof and application thereof in preventing and controlling plant diseases, belonging to the technical field of agricultural chemistry. The preparation method is that tetrahydrogeranyl halide and corresponding phosphine reagent are subjected to reflux reaction in an organic solvent, so that the preparation method is high in yield and simple in process. The compound, in particular to tetrahydrogeranyl triphenyl quaternary phosphonium salt, has excellent inhibitory activity on various plant pathogenic fungi such as banded sclerotial blight bacteria, pinus solani, tobacco black shank bacteria and the like, wherein the IC 50 of tetrahydrogeranyl triphenyl phosphonium chloride on the pinus solani is as low as 0.95 mg/L, and the effect is obviously better than that of control pesticide chlorothalonil. The invention provides a new candidate compound for developing a novel agricultural bactericide which is efficient, low in toxicity and derived from natural products.

Inventors

• CHEN YIXIN
• QIU XIAOYANG
• LIU SHUJUAN
• CHEN XINRAN
• YE BINHAO

Assignees

• 宁波大学科学技术学院

Dates

Publication Date

20260512

Application Date

20260202

Claims (10)

1. 1. A tetrahydrogeranyl quaternary phosphonium salt compound characterized by having the structure shown in the following general formula: A general formula I: and (2) a general formula II: Wherein X is any one of Cl, br and I.
2. 2. The tetrahydrogeranyl quaternary phosphonium salt compound according to claim 1, wherein said compound is selected from any one of tetrahydrogeranyl triphenyl phosphonium chloride, tetrahydrogeranyl triphenyl phosphonium bromide, tetrahydrogeranyl triphenyl phosphonium iodide, tetrahydrogeranyl tri-n-butyl phosphonium chloride, tetrahydrogeranyl tri-n-butyl phosphonium bromide, tetrahydrogeranyl tri-n-butyl phosphonium iodide.
3. 3. A process for preparing a tetrahydrogeranyl quaternary phosphonium salt compound according to claim 1 or 2, characterized by comprising the steps of: Carrying out nucleophilic substitution reaction on tetrahydrogeranyl halide and phosphine reagent in an organic solvent under the condition of heating reflux, and obtaining the quaternary phosphonium salt compound through post-treatment after the reaction is completed; Wherein the phosphine reagent is triphenylphosphine or tri-n-butylphosphine, and halogen in the tetrahydrogeranyl halide reacts with phosphorus atoms in the phosphine reagent.
4. 4. The method of claim 3, wherein the molar ratio of tetrahydrogeranyl halide to phosphine reagent is 1 (1.0-1.2); the organic solvent is ethyl acetate; the reaction temperature is the reflux temperature of the organic solvent, and the reaction time is 20-30 hours.
5. 5. Use of a tetrahydrogeranyl quaternary phosphonium salt compound according to claim 1 or 2 for the production of fungicides for combating phytopathogenic fungi.
6. 6. The method according to claim 5, wherein the plant pathogenic fungi are selected from at least one of Rhizoctonia solani, and Rhizoctonia solani.
7. 7. The use according to claim 5, wherein the tetrahydrogeranyl quaternary phosphonium salt compound is tetrahydrogeranyl triphenyl phosphonium chloride, tetrahydrogeranyl triphenyl phosphonium bromide or tetrahydrogeranyl triphenyl phosphonium iodide.
8. 8. An agricultural fungicidal composition comprising a fungicidally effective amount of a tetrahydrogeranyl quaternary phosphonium salt compound according to claim 1 or 2, and an agronomically acceptable carrier and/or adjuvant.
9. 9. The agricultural sterilization composition according to claim 8, wherein the formulation of the agricultural sterilization composition is wettable powder, water dispersible granule, emulsifiable concentrate or aqueous solution.
10. 10. The use according to claim 5 or 7, characterized in that the tetrahydrogeranyl triphenyl phosphonium chloride has a semi-inhibitory concentration IC 50 of less than 10 mg/L for controlling leptospora chrysosporium or leptospora tabaci.

Description

Tetrahydrogeranyl quaternary phosphonium salt compound and preparation method and application thereof Technical Field The invention relates to the technical field of agricultural chemistry, in particular to a novel quaternary phosphonium salt compound, a preparation method thereof and application of the compound as an agricultural bactericide in preventing and controlling plant pathogenic fungi. Background Plant diseases are one of the important factors restricting agricultural production. The problems of environmental pollution, pathogen resistance, pesticide residue and the like caused by long-term use of chemical synthesized pesticides are increasingly serious. Therefore, the development of a novel bactericide with high efficiency, low toxicity and environmental friendliness has become a current research hotspot. Quaternary ammonium salt antibacterial agents are well studied, but the problems of enhanced drug resistance and the like are also faced in long-term use. Quaternary phosphonium salts are a class of compounds similar in structure to quaternary ammonium salts but with a phosphorus atom as the center of positive charge. The radius of the phosphorus atom is larger than that of the nitrogen atom, so that the phosphorus atom has stronger polarization capability and is easier to combine with a cell membrane of a thallus with negative charges, thereby showing higher and wider antibacterial activity, having the potential advantages of low toxicity, small dosage and the like, and being a novel antibacterial agent with great development prospect. Citral is a natural monoterpene aldehyde widely existing in plant essential oil such as litsea cubeba, and has various biological activities such as antibacterial and antioxidant. However, aldehyde groups and olefinic bonds in the structure result in poor chemical stability and strong volatility, which limits its direct application. The structure modification is carried out on the citral, and the development of the stable and efficient derivative is an important way for improving the application value of the citral. At present, tetrahydrogeranyl (hydrogenated derivative of citral) is taken as a hydrophobic chain, combined with triphenylphosphine or tri-n-butylphosphine to construct novel quaternary phosphonium salt, and reports of the antibacterial activity of the quaternary phosphonium salt on various plant pathogenic fungi are systematically researched. Disclosure of Invention In view of this, the present invention aims to provide a series of tetrahydrogeranyl quaternary phosphonium salt compounds of novel structure. Another object of the present invention is to provide a simple and efficient process for producing the above-mentioned compounds. It is still another object of the present invention to provide the use of the above-mentioned compounds for controlling plant diseases, particularly plant diseases caused by fungi, which provides candidate compounds for developing novel plant-derived bactericides. The invention is realized by the following technical scheme: a tetrahydrogeranyl quaternary phosphonium salt compound having the structure shown in the following formula: A general formula I: and (2) a general formula II: Wherein X is any one of Cl, br and I. Further defined, the compound is selected from any one of tetrahydrogeranyl triphenyl phosphonium chloride, tetrahydrogeranyl triphenyl phosphonium bromide, tetrahydrogeranyl triphenyl phosphonium iodide, tetrahydrogeranyl tri-n-butyl phosphonium chloride, tetrahydrogeranyl tri-n-butyl phosphonium bromide, and tetrahydrogeranyl tri-n-butyl phosphonium iodide. The method for preparing the tetrahydrogeranyl quaternary phosphonium salt compound comprises the following steps: Carrying out nucleophilic substitution reaction on tetrahydrogeranyl halide and phosphine reagent in an organic solvent under the condition of heating reflux, and obtaining the quaternary phosphonium salt compound through post-treatment after the reaction is completed; Wherein the phosphine reagent is triphenylphosphine or tri-n-butylphosphine, and halogen in the tetrahydrogeranyl halide reacts with phosphorus atoms in the phosphine reagent. Further defined, the molar ratio of tetrahydrogeranyl halide to phosphine reagent is 1 (1.0-1.2); the organic solvent is ethyl acetate; the reaction temperature is the reflux temperature of the organic solvent, and the reaction time is 20-30 hours. The application of the tetrahydrogeranyl quaternary phosphonium salt compound in preparing a bactericide for preventing and treating plant pathogenic fungi, wherein the plant pathogenic fungi are at least one selected from the group consisting of rhizoctonia solani, campylobacter sojae, tobacco black shank and watermelon fusarium wilt. The tetrahydrogeranyl quaternary phosphonium salt compound is tetrahydrogeranyl triphenyl phosphonium chloride, tetrahydrogeranyl triphenyl phosphonium bromide or tetrahydrogeranyl triphenyl phosphonium iodide. An agricultura