CN-119684122-B - Pinene analogue containing ester group and preparation and application thereof

Abstract

The invention discloses a pinene analogue containing an ester group, and preparation and application thereof, and belongs to the field of agricultural chemicals. The structural formula of the pinene analogue containing the ester group is shown as formula I: the invention obtains a pinene analogue containing ester group by esterifying and modifying the aphid alarm pheromone pinene, and discovers that the compound has double functions of repelling aphids and attracting natural enemies of the aphids through biological activity research, and has good application prospect in green prevention and control of the aphids.

Inventors

• QIN YAOGUO
• HUANG YIWEN
• YANG XINLING
• LIU YAN
• ZHANG GUODONG

Assignees

• 中国农业大学

Dates

Publication Date

20260508

Application Date

20241217

Claims (14)

1. 1. A compound of formula I: In the formula I, R is a substituent group on a benzene ring and is monosubstituted; R is independently selected from any one of halogen, nitro, amino, C 1 -C 10 alkoxy, C 1 -C 10 straight or branched alkyl and halogen substituted C 1 -C 10 straight or branched alkyl.
2. 2. A compound of formula I in accordance with claim 1 wherein R is selected from any one of halogen, C 1 -C 10 straight or branched chain alkyl, C 1 -C 10 alkoxy, nitro, amino and trifluoromethyl.
3. 3. A compound of formula I in accordance with claim 2 wherein R is selected from methyl, propyl, isopropyl, methoxy, fluoro, chloro, bromo, amino, trifluoromethyl or nitro.
4. 4. The compound of formula I in claim 1, wherein the compound of formula I is selected from any one of the following: 。
5. 5. A process for the preparation of a compound of formula I according to any one of claims 1 to 3, comprising the steps of: in the presence of a dehydrating agent and a catalyst, carrying out esterification condensation reaction on the formula III and the formula IV to obtain a compound shown in the formula I; in formula IV, the definition of R is the same as the definition of R in formula I in any one of claims 1 to 3.
6. 6. The method according to claim 5, wherein the molar ratio of the dehydrating agent to the catalyst is 1:1-10:1-10:0.1-10; the dehydrating agent is at least one of N, N-diisopropyl carbodiimide, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide; The catalyst is at least one selected from 4-dimethylaminopyridine and 1-hydroxybenzotriazole; the esterification condensation reaction is carried out in an organic solvent.
7. 7. The method according to claim 6, wherein the organic solvent is at least one selected from cyclohexane, hexane, tetrahydrofuran, methylene chloride, 1, 4-dioxane, ethyl acetate, petroleum ether, methanol, ethanol, n-propanol, carbon tetrachloride, DMF, chloroform, diethyl ether and acetonitrile.
8. 8. The process according to claim 5 or 6, wherein the condensation reaction is carried out at a temperature of-50 ℃ to 200 ℃ for a period of 2 to 24 hours.
9. 9. The application of the compound shown in the formula I in aphid behavior control; In the formula I, R is a substituent group on a benzene ring and is monosubstituted; R is independently selected from any one of halogen, C 1 -C 10 alkoxy and C 1 -C 10 straight or branched alkyl.
10. 10. The method according to claim 9, wherein the aphid is at least one of the group consisting of Aphis persicae, aphis sojae, aphis fistulosa, aphis pisum, aphis cermets, and Aphis graminifolia.
11. 11. The application of the compound shown in the formula I in controlling aphid natural enemy behaviors; In the formula I, R is a substituent group on a benzene ring and is monosubstituted; R is independently selected from any one of amino, C 1 -C 10 alkoxy, C 1 -C 10 linear or branched alkyl, and halogen substituted C 1 -C 10 linear or branched alkyl.
12. 12. The method according to claim 11, wherein the natural enemies of aphids are Aphis gifuensis and/or Aleurites variegatus.
13. 13. An aphid behavior control agent, the active ingredient of which is a compound shown in a formula I; In the formula I, R is a substituent group on a benzene ring and is monosubstituted; R is independently selected from any one of halogen, C 1 -C 10 alkoxy and C 1 -C 10 straight or branched alkyl.
14. 14. An aphid natural enemy behavior control agent, the active ingredient of which is a compound shown in a formula I; In the formula I, R is a substituent group on a benzene ring and is monosubstituted; R is independently selected from any one of amino, C 1 -C 10 alkoxy, C 1 -C 10 linear or branched alkyl, and halogen substituted C 1 -C 10 linear or branched alkyl.

Description

Pinene analogue containing ester group and preparation and application thereof Technical Field The invention relates to the field of agricultural chemicals, in particular to a pinene analogue containing ester groups, a preparation method thereof and application of the pinene analogue in aphid control and natural enemy attraction. Background Aphids are worldwide agricultural pests and have the characteristics of multiple varieties, high propagation speed, overlapping generations and multiple hosts. At present, the control of aphids still depends on chemical pesticides, however, the drug resistance of aphids is more serious caused by using traditional pesticides for a long time. By 2024, myzus persicae (Myzus persicae) has been resistant to over 80 insecticide active ingredients, the top 10 of the most resistant invertebrate organisms worldwide. Therefore, development of novel aphid control agents which are green, safe and efficient is urgent. In recent years, biological control of aphids by natural enemies of aphids is favored by people because of the advantages of environmental friendliness and safety to non-target organisms. The cabbage aphid (DIAERETIELLA RAPAE) is a parasitic internally-consumed bee of a population of hymenoptera, aphididae and DIAERETIELLA, is used as an important natural enemy for biocontrol, has a very wide host range, mainly parasitizes various aphids of Aphis general families, such as aphids of Aphis erygii, aphis Raphani and Aphis brassicae, which harm crucifer crops, and plays a very important role in controlling the population number of aphids. After being attacked or stimulated by the outside world, the abdominal tube of the aphid can secrete small liquid drops, wherein the small liquid drops contain volatile gas with alarm activity, namely alarm pheromone, and other aphid individuals can receive alarm signals, generate behavioral reactions such as expelling and the like and quickly escape from the scene. The insect pest repellent or antifeedant effect can directly resist insect pests, and can also indirectly act by attracting natural enemies of the insect pests. Pinene (Pinene)The aphid alarm pheromone is an important aphid alarm pheromone component, can effectively repel the peach aphid, has good fumigation toxicity to the peach aphid, and can enhance the aphid repelling activity when being mixed with other terpenoid. In addition, pinene has attracting activity to various natural enemies of aphids, such as Chinese sand flies, green sand flies, thirteen-star ladybirds, heterodera and black stripe aphids. However, the biological activity of pinene and the like on natural enemies of Aphididae is still unknown, so that the behavior activity of the pinene and the like on parasitic wasps of aphids is worthy of further research, and the aphid control agent with the dual activities of aphid repellent and parasitic wasp attracting is expected to be developed. Although the aphid alarm pheromone component has the advantages of strong specificity, trace quantity and ecology friendliness, the aphid alarm pheromone component has the defects of easy volatilization, unstable structure and difficult application in fields. Therefore, the aphid control agent with the aphid alarm pheromone component as an active lead and with both activity and stability is developed, and has important significance for green control of aphids. Disclosure of Invention The invention aims to provide a pinene analogue containing ester groups and a preparation method and application thereof, the invention takes aphid alarm pheromone components as leads to synthesize the pinene analogue containing the ester groups, the compound has obvious aphid repelling activity and obvious aphid attracting activity, has double activity, and can be used for controlling crop, fruit tree, chinese herbal medicine and flower aphid. The structural formula of the pinene analogue containing the ester group is shown as formula I: In formula I: R represents a substituent on the benzene ring, which can be monosubstituted or polysubstituted; R can be independently selected from at least one of hydrogen, halogen, nitro, cyano, alkenyl (such as allyl-CH 2CHCH2), amino, C 1-C10 alkoxy, acyl (which can be specifically formyl-CHO, acetyl-COCH 3), aryl heteroaryl, heterocyclyl, carboxyl, ester (which can be specifically COOCH 3)、C1-C10 straight or branched alkyl, halogen substituted C 1-C10 straight or branched alkyl, halogen substituted C 1-C10 alkoxy). When R is a ring structure, R is connected with the benzene ring by a single bond or a parallel benzene ring; Specifically, R is mono-substituted or poly-substituted, and R is independently selected from at least one of methyl, isopropyl, formyl (-CHO), ester (-COOCH 3), methoxy, allyl-CH 2CHCH2, 3, 4-methylenedioxy, 3, 4-pyrrolyl, acetyl-COCH 3、Cl、F、-NO2、-CF3、-OCF3, ethoxy, br, H and carbonyl trifluoromethyl. The compound shown in the formula I is characterized in that R is monosubstituted; R is sele