CN-121990909-A - Synthesis method of hexadecatrienol acetate compound and application of hexadecatrienol acetate compound as litchi pedicle-borer sex pheromone attractant

Abstract

The invention discloses a synthesis method of hexadecatrienol acetate compounds and application of the hexadecatrienol acetate compounds as sex pheromone attractant for litchi pedicel borers. The invention adopts a convergent synthesis strategy to successfully prepare the 4-trans, 6-cis, 10-cis-hexadecatrienol acetate and the 4-trans, 6-trans, 10-cis-hexadecatrienol acetate, which not only remarkably improves the synthesis efficiency, but also has the characteristic of green and clean, and the invention also provides the application of the hexadecatrienol acetate compound as the sex pheromone attractant for the litchi fruit borers, which can be effectively used for monitoring, green prevention and control of the litchi fruit borers, reduce the use of chemical pesticides and ensure the quality safety of fruits and sustainable development of ecological environment.

Inventors

• YAO HONGLIANG
• MENG XIANG
• LI GANG
• ZHANG YALI
• CHEN DASONG

Assignees

• 广东省科学院动物研究所

Dates

Publication Date

20260508

Application Date

20260130

Claims (8)

1. 1. The synthesis method of the hexadecatrienol acetate compound is characterized in that the hexadecatrienol acetate compound is 4-trans, 6-cis, 10-cis-hexadecatrienol acetate or 4-trans, 6-trans, 10-cis-hexadecatrienol acetate; The synthesis method comprises the following steps: preparation of bromine-containing unsaturated alcohol: (1) Taking a compound 1 as a reaction raw material, and introducing acetylene gas into a mixed solvent system containing bromide and a palladium catalyst for addition reaction to obtain a bromine-substituted unsaturated intermediate, namely a compound 2; (2) Carrying out reduction reaction on the compound 2 to obtain bromine-containing unsaturated alcohol, namely a compound 3; ; Preparation of alkynyl-containing unsaturated compounds: (1) Taking a compound 4 as a raw material, and obtaining an unsaturated aldehyde intermediate, namely a compound 5 through oxidation reaction; (2) Mixing the compound 5 with dimethyl (1-diazonium-2-oxopropyl) phosphonate, and reacting in the presence of potassium carbonate to obtain an alkynyl-containing unsaturated compound, namely a compound 6; ; preparation of alkynol intermediates: reacting the compound 6 with the compound 3 in a system of a palladium catalyst, a copper salt catalyst and an amine solvent to obtain an alkynol intermediate, namely a compound 7; ; when the hexadecatrienol acetate compound is 4-trans, 6-cis, 10-cis-hexadecatrienol acetate: (1) Carrying out hydrogenation reaction on the compound 7 in the presence of a Lindlar catalyst to obtain a compound 8; (2) Carrying out an acylation reaction on the compound 8 to obtain a compound 9, namely 4-trans, 6-cis, 10-cis-hexadecatrienol acetate; ; when the hexadecatrienol acetate compound is 4-trans, 6-trans and 10-cis-hexadecatrienol acetate: (1) Reducing the compound 7 in a liquid ammonia reduction system of sodium to obtain a compound 10; (2) Carrying out acylation reaction on the compound 10 to obtain a compound 11, namely 4-trans, 6-trans, 10 cis-hexadecatrienol acetate; 。
2. 2. The method according to claim 1, wherein the step of preparing the alkynyl-containing unsaturated compound comprises an oxidation reaction using a mixed system of FeCl 3 and hydrogen peroxide.
3. 3. The process according to claim 1, wherein the hydrogenation reaction is carried out at a temperature of 70 ℃ for a period of 4 hours.
4. 4. The preparation method according to claim 1, wherein the temperature at which the compound 7 is reduced in a liquid ammonia reduction system of sodium is 0 ℃.
5. 5. The application of the hexadecatrienol acetate compound as the sex pheromone attractant for the litchi pedicel borers is characterized in that the hexadecatrienol acetate compound is one or two of 4-trans, 6-cis, 10-cis-hexadecatrienol acetate and 4-trans, 6-trans, 10-cis-hexadecatrienol acetate.
6. 6. The use according to claim 5, wherein the litchi pedicle screw moth sex pheromone attractant is used to attract litchi pedicle screw moth male adults.
7. 7. The method according to claim 5, wherein the mass ratio of 4-trans, 6-cis, 10-cis-hexadecatrienol acetate to 4-trans, 6-trans, 10-cis-hexadecatrienol acetate is (1-9): 9-1.
8. 8. The use according to claim 7, wherein the mass ratio of 4-trans, 6-cis, 10-cis-hexadecatrienol acetate to 4-trans, 6-trans, 10-cis-hexadecatrienol acetate is (3-7): 7-3.

Description

Synthesis method of hexadecatrienol acetate compound and application of hexadecatrienol acetate compound as litchi pedicle-borer sex pheromone attractant Technical Field The invention relates to the technical field of agricultural pest control, in particular to a synthesis method of hexadecatrienol acetate compounds and application of the hexadecatrienol acetate compounds as a sex pheromone attractant for litchi pedicel borers. Background The litchi industry takes an important role in agricultural economy, and along with the optimization of litchi varieties and the promotion of large-scale planting, the yield and the quality are steadily improved, but the difficult problem of pest control is not thoroughly solved all the time, and becomes a key factor for restricting the high-quality development of the industry. The litchi pedicel moths are one of the most serious pests in litchi producing areas, and damage to tender leaves, spikes and fruits of litchi, which cause leaf wilting, spike necrosis and fruit rot, directly affect the yield and commodity value of litchi, and cause great economic loss to farmers. At present, the prevention and control of the litchi fruit borers still depend on the traditional means, and have the defects that on one hand, biological prevention and control are limited by the number of natural enemies, environmental conditions and other factors, the prevention and control effect is unstable and is difficult to meet the prevention and control requirements of large-scale planting, and on the other hand, chemical pesticide prevention and control are widely applied at present, but long-term abuse of chemical pesticide can not only lead to drug resistance of the litchi fruit borers, but also cause the exceeding of pesticide residues of fruits, threaten food safety, and simultaneously destroy ecological environment and influence agricultural sustainable development. Therefore, the development of a safe, efficient and environment-friendly green prevention and control technology for the litchi pedicel borers has become an urgent requirement for the development of the litchi industry. The insect pheromone prevention and control technology has the outstanding advantages of economy, effectiveness, environmental friendliness, no harm to natural enemies, no pesticide residue and the like, and becomes one of the core directions of a plant disease and insect pest green prevention and control system. In recent years, researches on the sex pheromone of the litchi pedicel borer have been advanced to a certain extent, and partial results are obtained in the aspects of screening host volatile matters, identifying sex pheromone components, detecting antenna electrophysiology and the like. However, the pheromone compound screened by the existing research has a plurality of technical bottlenecks that the biosynthesis process is complex, the production efficiency is low due to complicated reaction steps, the partial synthesis route depends on heavy metal oxidants, environmental pollution is easy to cause, the environment is not in line with the green production concept, meanwhile, the pheromone compound has the problems of undefined action target, insufficient proportion optimization and the like, so that the attractive activity of the pheromone compound is unstable, and the large-scale popularization and application in the field cannot be realized. In conclusion, the existing litchi pedicle borer prevention and control technology has obvious defects, and the existing pheromone related research has not solved the core contradiction between the synthesis technology and practical application. Therefore, the development of the simple, environment-friendly and efficient synthesis method of the litchi Di moth sex pheromone compound has important significance for promoting the breakthrough of the green prevention and control technology of the litchi Di moth and guaranteeing the high-quality sustainable development of the litchi industry. Disclosure of Invention The invention aims to provide a synthesis method of hexadecatrienol acetate compounds and application of the hexadecatrienol acetate compounds as a litchi pedicle-borer sex pheromone attractant, so as to solve the problems in the prior art. In order to achieve the above object, the present invention provides the following solutions: The invention provides a synthesis method of a hexadecatrienol acetate compound, wherein the hexadecatrienol acetate compound is 4-trans, 6-cis, 10-cis-hexadecatrienol acetate or 4-trans, 6-trans, 10-cis-hexadecatrienol acetate; the structural formula of the 4-trans, 6-cis, 10-cis-hexadecatrienol acetate is as follows: ; the structural formula of the 4-trans, 6-trans, 10-cis-hexadecatrienol acetate is as follows: ; The synthesis method comprises the following steps: preparation of bromine-containing unsaturated alcohol: (1) Taking a compound 1 as a reaction raw material, and introducing acetylene gas into a mixed solvent system