WO2023072285A1 - 一种含芳香环的烯酸酯类化合物及其制备与应用 - Google Patents

一种含芳香环的烯酸酯类化合物及其制备与应用 Download PDF

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WO2023072285A1
WO2023072285A1 PCT/CN2022/128593 CN2022128593W WO2023072285A1 WO 2023072285 A1 WO2023072285 A1 WO 2023072285A1 CN 2022128593 W CN2022128593 W CN 2022128593W WO 2023072285 A1 WO2023072285 A1 WO 2023072285A1
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aphid
compound
control
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杨新玲
潘世香
杨朝凯
刘彦
秦耀果
凌云
石卓
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中国农业大学
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/86—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with esterified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/54—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/64—Oxygen atoms

Definitions

  • the invention belongs to the field of agricultural chemicals, and in particular relates to an aromatic ring-containing enoic acid ester compound and a preparation method thereof, as well as the application of the compound in aphid control and plant disease control.
  • Pesticides are a powerful tool to ensure stable and high yields of grain, and can recover 20-50% of the losses caused by diseases, insect pests and weeds every year.
  • many problems have been brought about: drug resistance, environmental pollution, and the safety of non-target organisms, which have aroused widespread concern. Therefore, it is imminent to carry out the creation of eco-friendly new pesticides.
  • Aphids belong to the superfamily Aphidoidea of the order Homoptera. They have the characteristics of many types, fast reproduction, wide range of hosts, and easy to produce drug resistance. They are very important agricultural pests (Wang, G.-P et al. J. Integr . Plant. Biol. 2015, 57, 770.). Most of the chemical agents currently used for aphid control have resistance problems or safety problems for non-target organisms, especially because of their toxicity to bees and are banned (Butler D. Nature, 2018.). Therefore, it is of far-reaching significance to find new safe and effective aphid control agents on the premise of ecological security.
  • carvacrol and thymol have a broad antibacterial spectrum and strong activity, and have the potential for development and application as botanical fungicides;
  • Pathogenic fungi have inhibitory effects and can be used as synergists in plant disease control (Hou Huiyu et al., Journal of Plant Protection, 2020, 47(06): 1362-1369;
  • the object of the present invention is to provide a kind of enoic acid ester compound containing aromatic ring and its preparation and application.
  • the present invention uses natural products as raw materials to synthesize the enoic acid ester compound containing aromatic ring. It has a poisonous effect and has an inhibitory effect on plant pathogenic bacteria, and can be used as an eco-friendly agent for the prevention and control of agricultural pests and diseases.
  • the aromatic ring-containing enoate compound provided by the present invention has a structural formula as shown in formula I-a, formula I-b or formula I-c:
  • n is an integer from 0 to 2, specifically 0, 1 or 2;
  • R 1 represents a substituent on the benzene ring, which can be mono-substituted or multi-substituted, and R 1 can be independently selected from hydrogen, halogen, nitro, cyano, alkenyl (such as allyl-CH 2 CHCH 2 ), C1 ⁇ C8 alkoxy group, acyl group (specifically formyl-CHO, acetyl-COCH 3 ), heteroaryl, heterocyclic group, carboxyl, ester group (specifically COOCH 3 ), C1 ⁇ C8 straight chain or branched At least one of the group consisting of chain alkyl, halogen substituted C1 ⁇ C8 straight chain or branched chain alkyl, halogen substituted C1 ⁇ C8 alkoxy;
  • R 1 is a ring structure, R 1 and the benzene ring are connected by a single bond or an acene ring;
  • R 1 is mono-substituted or multi-substituted, and R 1 is independently methyl, isopropyl, formyl (-CHO), ester (-COOCH 3 ), methoxy, allyl-CH 2 CHCH 2 , 3,4-methylenedioxy, 3,4-pyrrolyl, acetyl-COCH 3 , Cl, F, -NO 2 , -CF 3 , -OCF 3 , ethoxy, Br, H, carbonyl at least one of trifluoromethyl.
  • the compound shown in formula I-a can specifically be any of the following:
  • the compound shown in formula I-b can specifically be any of the following:
  • the compound shown in formula I-c can specifically be any of the following:
  • the present invention also provides preparation methods of the compounds represented by the above formula I-a, formula I-b, and formula I-c.
  • the preparation method of the compounds shown in formula I-a, formula I-b, and formula I-c provided by the present invention comprises the following steps: in an organic solvent, the compounds shown in formula II-a, formula II-b, and formula II-c are respectively mixed with formula The compound shown in III undergoes an esterification condensation reaction to obtain compounds shown in formula I-a, formula I-b, and formula I-c;
  • n and R in formula III are the same as m and R in formula Ia;
  • the organic solvent can be selected from cyclohexane, hexane, tetrahydrofuran, dichloromethane, 1,4-dioxane, ethyl acetate, petroleum ether, methanol, ethanol, n-propanol, At least one or any combination of two or more of carbon tetrachloride, DMF, chloroform, diethyl ether, and acetonitrile;
  • a condensation reagent is also added to activate the carboxyl group in the compound shown in the formula II;
  • the condensation reagent may be at least one of DIC, DIEA, DCC, DMAP, EDCI and HOBt.
  • the temperature of the esterification condensation reaction can be -10-80°C, preferably the reaction temperature can be 10-40°C, and the time can be 2-24 hours, preferably the reaction time can be 8 hours, 4-40°C. 8 hours, 8-12 hours or 10-20 hours;
  • the molar ratio of the compound represented by the formula II-a, II-b or II-c to the compound represented by the formula III can be 1:1 ⁇ 10, specifically 1:1.5, 1:1.5 ⁇ 10, 1 :1 ⁇ 1.5, 1:1 ⁇ 5 or 1:1 ⁇ 7.5.
  • the reaction product is obtained through column chromatography purification.
  • the aphid behavior control refers to the repelling behavior control of aphids
  • aphid specifically can be peach aphid or apple yellow aphid
  • the plant diseases may be diseases caused by Pythium melon and fruit, sheath blight of rice, Sclerotinia sclerotiorum and rice blast fungus.
  • the medicine can specifically be an aphid control agent, an aphid behavior control agent or a plant disease control agent.
  • the aromatic ring-containing enoic acid ester compound of the present invention has been proved by tests to have obvious aphidicidal activity, repellent activity and bactericidal activity, that is, it has direct chemical control effect on aphids, and also has the activity of regulating the behavior of aphids, and can be used as aphids
  • the control agent is used to prevent and control crops, fruit trees, Chinese herbal medicine and flower aphids; it can also be used in the prevention and control of plant diseases.
  • the raw material of the invention is derived from natural substances, the preparation method is simple and easy, the product is easy to purify, the cost is low, it is environmentally friendly and eco-friendly, and some compounds have excellent insecticidal activity, repellent activity and bactericidal activity.
  • the green prevention and control of diseases has a good application prospect.
  • the research on biological activity proves that the invention provides a green and safe plant protection product with dual functions of insect repelling and antibacterial.
  • Method 1 Take a 100ml single-necked flask, add 0.60g (6mmol) 3-methyl-2-butenoic acid and 25mL tetrahydrofuran, then add 1.03g (9mmol) DIC and 0.07g (0.6mmol) DMAP, and stir at room temperature for 1h. Subsequently, 15 mL of tetrahydrofuran solution containing 0.90 g (6 mmol) of 5-isopropyl-2-methylphenol was added dropwise to the above reaction solution, and reacted at room temperature for 8 h.
  • Method 2 Take a 100ml single-necked flask, add 0.60g (6mmol) 3-methyl-2-butenoic acid and 25mL dichloromethane, then add 1.49g (7.2mmol) DCC and 0.07g (0.6mmol) DMAP, and stir at room temperature Reaction 0.5h. Then, 15 mL of dichloromethane solution containing 0.90 g (6 mmol) of 5-isopropyl-2-methylphenol was added dropwise to the above reaction liquid, and reacted at room temperature for 6 h.
  • Method 3 Take a 100ml single-necked flask, add 0.60g (6mmol) 3-methyl-2-butenoic acid and 25mL dichloromethane, then add 1.38g (7.2mmol) EDCI and 0.41g (3mmol) HOBt, and stir the reaction at room temperature 1h. Then, 15 mL of dichloromethane solution containing 0.90 g (6 mmol) of 5-isopropyl-2-methylphenol was added dropwise to the above reaction liquid, and reacted at room temperature for 6 h.
  • Embodiment 2 the preparation of 5-isopropyl-2-methylphenyl-(E)-3,7-dimethyloctyl-2,6-dienoate (I-b-27)
  • Step 3 Preparation of 5-isopropyl-2-methylphenyl-(E)-3,7-dimethyloctyl-2,6-dienoate (I-b-27)
  • Embodiment 3 the insecticidal activity of compound of the present invention to aphids
  • Some compounds of the present invention were used as representatives of the examples (as shown in Tables 3 and 4) to test their insecticidal activity against aphids.
  • the insecticidal activity test for the apple yellow aphid was consistent with the insecticidal activity test for the green peach aphid except that the cabbage leaves were replaced with crabapple leaves.
  • the criteria for judging the death are: touch the insect body lightly, and those who do not move at all are considered dead.
  • Corrected mortality rate (%) (mortality rate of treatment group - mortality rate of blank group) / (1 - mortality rate of blank group) * 100%
  • Table 3 results show that the compound of the present invention has killing activity to aphids at high concentrations, and wherein compound I-b-30, I-b-33 and I-b-38 are all at 70% to the suppression death rate of peach aphid under the dosage of 300mg/L More than %; Table 4 result shows, compound I-b-27, I-b-28 and I-b-34 are all more than 90% to the suppression mortality of apple yellow aphid under the dosage of 300mg/L, have the value of further developing as aphid control agent .
  • Embodiment 4 the repellent activity of the compounds of the present invention to aphids
  • Some compounds of the present invention were used as representatives of the examples (as shown in Table 5) to test their repellent activity against aphids.
  • the test equipment is a self-made T-shaped olfactometer in our laboratory. More than 20 wingless adult aphids are released from the release port, and moist air with activated carbon and distilled water is introduced into each arm through an air pump at 0.2 L/min. The moist air introduced by the test arm first passes through 5 ⁇ g of the sample odor source, and the other arm is used as the control arm, and the introduced moist air first passes through the solvent. Record the number of aphids in each arm when the sample was introduced for 15 minutes.
  • the olfactometer and leather tube were cleaned with absolute ethanol, the filter paper was replaced, and the two arms were used interchangeably.
  • Each sample experiment was repeated at least three times. The aphids that crossed the center of the olfactometer were included in the treatment group or the control group, and the aphids that did not cross were recorded as the unresponsive group.
  • Repellent rate (the number of insects in the control group - the number of insects in the treatment group) / (the number of insects in the control group + the number of insects in the treatment group) * 100%
  • Table 5 show that the compounds of the present invention have repellent activity to peach aphids at low concentrations, wherein compounds I-b-05, I-b-17, I-b-33, I-b-37, I-b-38, I-c-03 and I-c-10 At a dose of 5 ⁇ g, the repellent rate against peach aphids is above 60%.
  • the synthesis of the above-mentioned compounds is simple and feasible, and the source of raw materials is green, safe, and eco-friendly. It has the value of further development as an aphid behavior control agent and has a good application prospect.
  • Embodiment 5 the inhibitory activity of compound of the present invention to plant pathogenic bacteria
  • Some compounds of the present invention were used as representatives of the examples (as shown in Table 6) to conduct in vitro antibacterial activity tests on various plant pathogenic bacteria.
  • the tested strains were Pythium spp. of melon and fruit, sheath blight of rice, Sclerotinia sclerotiorum and rice blast fungus.
  • the invention has good activity on various pathogenic bacteria in the field of pesticides, and can be used as a fungicide for the prevention and control of the above-mentioned plant pathogenic bacteria.
  • the compound of the present invention is dissolved in dimethyl sulfoxide, and prepared into a 10000 ⁇ g/ml liquid medicine for future use. Take 1ml of the spare medicinal solution and mix it with 199ml of PDA medium to prepare a toxic medium with a concentration of 50 ⁇ g/ml. Pour it into a petri dish with a diameter of 90cm, about 15ml per dish. After it solidifies, insert the activated pathogenic fungus cake and place it in an incubator at 25°C for cultivation. Dimethyl sulfoxide is used as a solvent control. Sterile water was used as the blank control, and each sample was repeated 3 times. The above operation was a strict aseptic operation. After the blank control colony had grown sufficiently, the diameter of the colony of each treatment was measured by the cross method, and the average value was taken. The mycelial growth inhibition rate was calculated according to the following formula:
  • Table 6 shows the in vitro bactericidal activity data of some representative compounds of the present invention against Pythium melon and fruit, rice sheath blight, Sclerotinia sclerotiorum and rice blast fungus.
  • the aromatic ring-containing enoic acid ester compound of the present invention has been proved by tests to have obvious aphidicidal activity, repellent activity and bactericidal activity, that is, it has direct chemical control effect on aphids, and also has the activity of regulating the behavior of aphids, and can be used as aphids
  • the control agent is used to prevent and control crops, fruit trees, Chinese herbal medicine and flower aphids; it can also be used in the prevention and control of plant diseases.
  • the raw material of the invention is derived from natural substances, the preparation method is simple and easy, the product is easy to purify, the cost is low, it is environmentally friendly and eco-friendly, and some compounds have excellent insecticidal activity, repellent activity and bactericidal activity.
  • the green prevention and control of diseases has a good application prospect.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

本发明公开了一种含芳香环的烯酸酯类化合物及其制备与应用。本发明的化合物结构简单，易于合成，合成原料源于天然产物，对环境无公害，生态友好。本发明提供的化合物对蚜虫具有较好的驱避和杀死作用，同时对植物病原菌有很好的抑制活性，可作为蚜虫控制剂及杀菌剂，在害虫及植物病害的绿色防控方面具有良好的应用前景。

Description

一种含芳香环的烯酸酯类化合物及其制备与应用 技术领域
本发明属于农用化学品领域，具体涉及一种含芳香环的烯酸酯类化合物及其制备方法，以及该类化合物在蚜虫防治及植物病害防治方面的应用。
背景技术
农药是保证粮食稳产丰产的有力工具，每年可挽回因病虫草害造成的损失达20-50％。但是随着传统农药的不断使用，带来了诸多问题：抗药性、环境污染以及对非靶标生物安全等，引起人们广泛关注。因此，进行生态友好的新农药的创制迫在眉睫。
蚜虫属于同翅目蚜总科(Aphidoidea)，具有种类多、繁殖快、寄主广、易产生抗药性等特点，是一类非常重要的农业害虫(Wang,G.-P et al.J.Integr.Plant.Biol.2015,57,770.)。目前用于蚜虫防治的化学药剂大多存在着抗性问题或对非靶标生物的安全问题等，尤其是因对蜜蜂的毒性而被禁用(Butler D.Nature,2018.)。因此如何以生态安全为前提，寻找新的安全有效的蚜虫控制剂具有深远的意义。
天然产物一直是科研工作者进行药物开发的宝库，在自然界中也存在着许多对蚜虫具有拮抗作用的物质。研究发现，丁香酚(式1)和香芹酚(式2)具有良好的杀蚜活性，此外香芹酚、百里香酚(式3)和水杨酸甲酯(式4)具有良好的驱避蚜虫活性；反-(β)-法尼烯(式5)、香叶醇(式6)及法尼醇(式7)对蚜虫也具有良好的驱避活性且在高浓度下有杀蚜活性，其结构分别如式1-7所示。(Pettersson J,et al.Journal of Chemical Ecology,1994,20(10)，2565-2574；Isman,et al.Crop protection,2000,19(8-10):603-608；Webster B,et al.Animal Behaviour,2010,79(2):451-457.)我们关注到两类对蚜虫有生物活性的天然物质，一类为对蚜虫有生物活性的天然酚类物质，另一类为含有2-甲基-2丁烯结构单元的萜烯类物质。有趣的是这两类物质在植物病害的防治中也发挥着重要的作用：香芹酚及百里香酚抑菌谱广且活性强，具有作为植物源杀菌剂的开发应用的潜力；法尼醇对病原真菌具有抑制作用且可作为增效剂在植物病害防治中应用(侯辉宇等,植物保护学报,2020,47(06):1362-1369；中国发明专利:ZL201810279381.X,ZL201810279382.4,ZL201810759419.3，ZL201810279387.7)。
Figure PCTCN2022128593-appb-000001
发明公开
本发明的目的是提供一种含芳香环的烯酸酯类化合物及其制备与应用，本发明以天然产物为原料合成得到含芳香环的烯酸酯类化合物，该化合物对蚜虫具有驱避及毒杀作用且对植物病原菌具有抑制作用，可以作为生态友好的药剂用于农业害虫及病害的防治。
本发明所提供的含芳香环的烯酸酯类化合物，其结构式如式I-a、式I-b或式I-c所示：
Figure PCTCN2022128593-appb-000002
式I-a、式I-b、式I-c中：
m为0～2的整数，具体可为0、1或2；
R 1表示苯环上的取代基，可为单取代或多取代，R 1可独立地选自由氢、卤素、硝基、氰基、烯基(如烯丙基-CH 2CHCH 2)，C1～C8烷氧基、酰基(具体可为甲酰基-CHO、乙酰基-COCH 3)、芳杂基、杂环基、羧基、酯基(具体可为COOCH 3)、C1～C8直链或支链烷基、卤素取代的C1～C8直链或支链烷基、卤素取代的C1～C8烷氧基组成的组中的至少一种；
当R 1为环结构时，R 1与苯环以单键或者并苯环连接；
具体地，R 1为单取代或多取代，R 1独立地为甲基、异丙基、甲酰基(-CHO)、酯基(-COOCH 3)、甲氧基、烯丙基-CH 2CHCH 2、3,4-亚甲二氧基、3,4-吡咯基、乙酰基-COCH 3、Cl、F、-NO 2、-CF 3、-OCF 3、乙氧基、Br、H、羰基三氟甲基中的至少一种。
式I-a所示化合物具体可为如下任意一种：
Figure PCTCN2022128593-appb-000003
Figure PCTCN2022128593-appb-000004
式I-b所示化合物具体可为如下任意一种：
Figure PCTCN2022128593-appb-000005
Figure PCTCN2022128593-appb-000006
式I-c所示化合物具体可为如下任意一种：
Figure PCTCN2022128593-appb-000007
本发明还提供了上述式I-a、式I-b、式I-c所示化合物的制备方法。
本发明所提供的式I-a、式I-b、式I-c所示化合物的制备方法，包括如下步骤：在有机溶剂中，将式Ⅱ-a、式Ⅱ-b、式Ⅱ-c所示化合物分别与式Ⅲ所示化合物进行酯化缩合反应，得到式I-a、式I-b、式I-c所示化合物；
Figure PCTCN2022128593-appb-000008
式III中的m和R 1与式I-a中的m和R 1相同；
上述的制备方法中，所述有机溶剂可选自环己烷、己烷、四氢呋喃、二氯甲烷、1,4-二氧六环、乙酸乙酯、石油醚、甲醇、乙醇、正丙醇、四氯化碳、DMF、氯仿、二乙醚、乙腈中的至少一种或两种及以上的任意组合；
所述酯化缩合反应中还加入缩合试剂活化所述式Ⅱ所示化合物中的羧基；
所述缩合试剂可为DIC、DIEA、DCC、DMAP、EDCI和HOBt中的至少一种。
上述的制备方法中，所述酯化缩合反应的温度可为-10～80℃，优选反应温度可为10～40℃，时间可为2～24小时，优选反应时间可为8小时、4～8小时、8～12小时或10～20小时；
所述式II-a、II-b或II-c所示化合物和所述式III所示化合物的摩尔比可为1:1～10，具体可为1:1.5、1:1.5～10、1:1～1.5、1:1～5或1:1～7.5。
上述的制备方法中，通过柱层析纯化得到反应产物。
上述式I-a、I-b或I-c所示化合物在蚜虫防治、蚜虫行为控制及植物病害防治中的应用也属于本发明的保护范围，
所述蚜虫行为控制指蚜虫的驱避行为控制；
所述蚜虫具体可为桃蚜或苹果黄蚜；
所述植物病害具体可为瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌引起的病害。
以式I-a、I-b或I-c所示含芳香环的烯酸酯类化合物为活性成分的药物也在本发明的保护范围之内。
所述药物具体可为蚜虫防治剂、蚜虫行为控制剂或植物病害防治剂。
本发明含芳香环的烯酸酯类化合物，经试验证实有明显的杀蚜活性、驱避活性和杀菌活性，即对蚜虫有直接的化学防治效果，还具有调控蚜虫行为的活性，可作为蚜虫控制剂，用于防治农作物、果树、中草药及花卉蚜虫；还可以应用于植物的病害防治中。
本发明原料来源于天然物质，制备方法简便易行，产物纯化容易，成本较低，对环境无公害，生态友好，部分化合物具有优异的杀虫活性、驱避活性及杀菌活性，在害虫和植物病害的绿色防控方面具有良好的应用前景。
经生物活性研究证明，本发明提供了具有防虫抗菌双重功能的绿色安全植物保护产品。
实施发明的最佳方式
下述实施例中的实验方法，如无特别说明，均为常规方法
下面结合实施例对本发明作进一步的说明，但不以任何方式对本发明加以限制，基于本发明教导所做的任何变更或改进，均属于本发明的保护范围。
实施例1、5-异丙基-2-甲基苯基-3-甲基丁-2-烯酸酯的制备(I-a-01)
方法1：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL四氢呋喃，然后加入1.03g(9mmol)DIC和0.07g(0.6mmol)DMAP，室温搅拌反应1h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的四氢呋喃溶液滴加至上述反应液中，室温反应 8h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率50.4％。
方法2：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL二氯甲烷，然后加入1.49g(7.2mmol)DCC和0.07g(0.6mmol)DMAP，室温搅拌反应0.5h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的二氯甲烷溶液滴加至上述反应液中，室温反应6h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率55.6％
方法3：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL二氯甲烷，然后加入1.38g(7.2mmol)EDCI和0.41g(3mmol)HOBt，室温搅拌反应1h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的二氯甲烷溶液滴加至上述反应液中，室温反应6h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率48.4％。
核磁氢谱数据如下： 1H NMR(500MHz,Chloroform-d)δ7.17–7.11(m,1H),7.00(dd,J＝7.8,1.8Hz,1H),6.87(d,J＝1.8Hz,1H),5.95(p,J＝1.4Hz,1H),2.93–2.81(m,1H),2.23(d,J＝1.3Hz,3H),2.13(s,3H),1.99(d,J＝1.4Hz,3H),1.23(d,J＝7.0Hz,6H)。
参考上述I-a-01的制备方法，可以制备得到式I-a系列化合物。
实施例2、5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯的制备(I-b-27)
步骤1：(E)-3,7-二甲基辛基-2,6-二烯醛的制备
Figure PCTCN2022128593-appb-000009
取300ml单口瓶，向其中加入4.62g(30mmol)(E)-3,7-二甲基辛基-2,6-二烯醇及100ml的二氯甲烷，冰浴下分批加入26.08g(300mmol)活性二氧化锰，室温反应12h。将反应液滴于砂芯漏斗中抽滤，用二氯甲烷和乙酸乙酯洗涤，减压脱去溶剂，得(E)-3,7-二甲基辛基-2,6-二烯 醛，产率95％。
步骤2：(E)-3,7-二甲基辛基-2,6-二烯酸的制备
向500ml单口瓶中加入2.57g(16.9mmol)(E)-3,7-二甲基辛基-2,6-二烯醛及27.5ml二甲基二丁烯和50ml丙酮，然后缓慢滴加由13.09g(144.7mmol)亚氯酸钠和22.4g(125.8mmol)二水磷酸二氢钠配成的100ml水溶液，滴加时间约0.5h，滴加完毕后室温继续反应1h。用50ml乙酸乙酯萃取三次，干燥脱溶后得(E)-3,7-二甲基辛基-2,6-二烯酸，产率92％。
步骤3：5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯(I-b-27)的制备
取100ml单口烧瓶，加入1.01g(6mmol)(E)-3,7-二甲基辛基-2,6-二烯酸及25mL的二氯甲烷中，随后将1.49g(7.2mmol)DCC和0.07g(0.6mmol)DMAP添加至单口烧瓶中，室温搅拌反应0.5h，随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL二氯甲烷溶液滴加至上述反应液中，室温反应8h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥、减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝100：1)，得5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯(I-b-27)，收率60.1％。 1HNMR(500MHz,Chloroform-d)δ7.14(d,J＝7.8Hz,1H),7.00(dd,J＝7.8,1.9Hz,1H),6.88(d,J＝1.9Hz,1H),5.94(d,J＝1.3Hz,1H),5.12(dddd,J＝6.9,5.5,2.9,1.5Hz,1H),2.87(hept,J＝6.9Hz,1H),2.29–2.19(m,7H),2.14(s,3H),1.71(d,J＝1.4Hz,3H),1.64(d,J＝1.4Hz,3H),1.24(s,3H),1.22(s,3H)。
参考上述制备方法，可以制备得到式I-b及I-c的系列化合物。
部分具体式I-a、I-b、I-c化合物的外观、熔点及收率列于表1中， 1H NMR谱的数据列于表2中。
表1式I-a、I-b、I-c部分化合物的熔点、外观和收率
Figure PCTCN2022128593-appb-000010
Figure PCTCN2022128593-appb-000011
Figure PCTCN2022128593-appb-000012
Figure PCTCN2022128593-appb-000013
表2式I-a、I-b、I-c部分化合物的核磁氢谱数据
Figure PCTCN2022128593-appb-000014
Figure PCTCN2022128593-appb-000015
Figure PCTCN2022128593-appb-000016
Figure PCTCN2022128593-appb-000017
实施例3、本发明化合物对蚜虫的杀虫活性
用本发明部分化合物作为实施例的代表(如表3、4所示)测试对蚜虫的杀虫活性。使用万分之一天平称取6mg样品，用0.6mL DMSO溶解，用移液枪吸取0.3mL药液注入20mL小烧杯中，并加入9.7mL曲拉通Triton X-100(5‰)水溶液配制成300mg/L溶液。将市场购买来的甘蓝叶用清水清洗干净并擦干后，并且用直径为15mm的打孔器打出合适大小的叶子，并浸入稀释的含有化学品溶液中20s后，将叶子自然干燥，待溶剂挥发后置于35mm的生测培养皿中，将叶子的背面向上翻转，并接入20头桃蚜，每个处理重复3次试验。置于温度为(25±1)℃的人工气候室中，48h后检查蚜虫死亡数。用加入0.3mL的DMSO和9.7mL曲 拉通水溶液作溶剂空白对照。
对于苹果黄蚜的杀虫活性测试除将甘蓝叶换为海棠叶外，其余与桃蚜杀虫活性测试一致。
死亡判断标准为：轻触虫体，以完全不动者为死亡。
校正死亡率(％)＝(处理组死亡率-空白组死亡率)/(1-空白组死亡率)*100％
杀桃蚜活性测试结果见表3；杀苹果黄蚜活性测试结果见表4。
表3部分式I-a、I-b、I-c化合物对桃蚜的杀虫活性(浓度300mg/L)
Figure PCTCN2022128593-appb-000018
表4部分式I-b化合物对苹果黄蚜的杀虫活性(浓度300mg/L)
Figure PCTCN2022128593-appb-000019
Figure PCTCN2022128593-appb-000020
表3结果表明，本发明的化合物在高浓度下对蚜虫具有杀死活性，其中化合物I-b-30、I-b-33和I-b-38在300mg/L的剂量下对桃蚜的抑制死亡率均在70％以上；表4结果表明，化合物I-b-27、I-b-28和I-b-34在300mg/L的剂量下对苹果黄蚜的抑制死亡率均在90％以上，具有作为蚜虫防治剂进一步开发的价值。
实施例4、本发明化合物对蚜虫的驱避活性
用本发明部分化合物作为实施例的代表(如表5所示)测试对蚜虫的驱避活性。测试设备为本实验室自制T型嗅觉仪，由释放口释放20头以上无翅成蚜，每臂经抽气泵以0.2L/min通入经活性炭及蒸馏水的潮湿空气。测试臂导入的潮湿空气先经过5μg样品味源物，另一臂作为对照臂，导入的潮湿空气先经过溶剂。记录导入样品15min时蚜虫在各臂的数目。每重复一次均用无水乙醇清洗嗅觉仪及皮管、更换滤纸片、且对调两臂使用，每个样品实验至少重复三次。以越过嗅觉仪中心为准计入处理组或对照组，未越过的蚜虫记为未反应组。
计算驱避率，公式如下所示
驱避率＝(对照组虫数-处理组虫数)/(对照组虫数+处理组虫数)*100％
蚜虫驱避活性测试结果见表5
表5部分式I-a、I-b、I-c化合物对桃蚜的驱避活性
Figure PCTCN2022128593-appb-000021
Figure PCTCN2022128593-appb-000022
表5结果表明，本发明的化合物在低浓度下对桃蚜具有驱避活性，其中化合物I-b-05、I-b-17、I-b-33、I-b-37、I-b-38、I-c-03和I-c-10在5μg的剂量下对桃蚜的驱避率均在60％以上，且上述化合物合成简便可行，原料来源绿色安全，生态友好，具有作为蚜虫行为控制剂进一步开发的价值，具有良好应用前景。
实施例5、本发明化合物对植物病原菌的抑制活性
用本发明部分化合物作为实施例的代表(如表6所示)对植物多种病原菌进行了离体抑菌活性测试。供试菌种为瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌。本发明对农药领域多种病原菌表现出很好的活性，可以作为杀菌剂用于上述植物病原菌的防治。
将本发明化合物溶于二甲基亚砜，配制成10000μg/ml的药液备用。取1ml备用药液与199ml PDA培养基混匀，制备成浓度为50μg/ml的含毒培养基。将其倒入直径为90cm的培养皿中，每皿大约15ml，待其固化后，接入活化好的病原真菌菌饼，置于25℃培养箱中培养，二甲基亚砜为溶剂对照，无菌水为空白对照，每个样品重复3次，以上操作为严格的无菌操作，待空白对照菌落充分生长后，以十字交叉法量取每个处理的菌落直径，取其平均值。按照以下公式计算菌丝生长抑制率：
Figure PCTCN2022128593-appb-000023
本发明部分代表化合物对瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌的离体杀菌活性数据见表6。
表6式I-a部分化合物的离体杀菌活性数据(50μg/mL)
Figure PCTCN2022128593-appb-000024
从表6可以看出，本发明提供的部分式I-a化合物对所测试的4种植物病原菌均具有一定的抑制活性。在50μg/mL浓度下，3个化合物对水稻纹枯病菌的抑制率超过85％。化合物I-a-03杀菌活性优异，对水稻纹枯病菌和油菜菌核病菌的抑制率均为100％。
工业应用
本发明含芳香环的烯酸酯类化合物，经试验证实有明显的杀蚜活性、驱避活性和杀菌活性，即对蚜虫有直接的化学防治效果，还具有调控蚜虫行为的活性，可作为蚜虫控制剂，用于防治农作物、果树、中草药及花卉蚜虫；还可以应用于植物的病害防治中。
本发明原料来源于天然物质，制备方法简便易行，产物纯化容易，成本较低，对环境无公害，生态友好，部分化合物具有优异的杀虫活性、驱避活性及杀菌活性，在害虫和植物病害的绿色防控方面具有良好的应用前景。

Claims (10)

  1. 式I-a、式I-b或式I-c所示化合物：
    Figure PCTCN2022128593-appb-100001
    式I-a、式I-b、式I-c中：
    m为0～2的整数；
    R 1表示苯环上的取代基，为单取代或多取代，
    R 1独立地选自由氢、卤素、硝基、氰基、烯基，C1～C8烷氧基、酰基、芳杂基、杂环基、羧基、酯基、C1～C8直链或支链烷基、卤素取代的C1～C8直链或支链烷基、卤素取代的C1～C8烷氧基组成的组中的至少一种；
    当R 1为环结构时，R 1与苯环以单键或者并苯环连接。
  2. 根据权利要求1所述的化合物，其特征在于：R 1为单取代或多取代，R 1独立地为甲基、异丙基、甲酰基、酯基、甲氧基、烯丙基、3,4-亚甲二氧基、3,4-吡咯基、乙酰基-COCH 3、Cl、F、-NO 2、-CF 3、-OCF 3、乙氧基、Br、H、羰基三氟甲基中的至少一种。
  3. 根据权利要求1或2所述的化合物，其特征在于：式I-a所示化合物为如下任意一种：
    Figure PCTCN2022128593-appb-100002
    Figure PCTCN2022128593-appb-100003
  4. 根据权利要求1或2所述的化合物，其特征在于：式I-b所示化合物为如下任意一种：
    Figure PCTCN2022128593-appb-100004
    Figure PCTCN2022128593-appb-100005
  5. 根据权利要求1或2所述的化合物，其特征在于：式I-c所示化合物为如下任意一种：
    Figure PCTCN2022128593-appb-100006
  6. 制备权利要求1-5中任一项所述的式I-a、式I-b、式I-c所示化合物的制备方法，包括如下步骤：在有机溶剂中，将式Ⅱ-a、式Ⅱ-b、式Ⅱ-c所示化合物分别与式Ⅲ所示化合物进行酯化缩合反应，得到式I-a、式I-b、式I-c所示化合物；
    Figure PCTCN2022128593-appb-100007
    式III中的m和R 1与权利要求1中式I-a中的m和R 1相同。
  7. 根据权利要求6所述的方法，其特征在于：所述酯化缩合反应中还加入缩合试剂；
    所述缩合试剂为DIC、DIEA、DCC、DMAP、EDCI和HOBt中的至少一种；
    所述酯化缩合反应的温度为-10～80℃，时间为2～24小时；
    所述式II-a、II-b或II-c所示化合物和所述式III所示化合物的摩尔比为1:1～10。
  8. 权利要求1-5中任一项所述的式I-a、式I-b、式I-c所示化合物在蚜虫防治、蚜 虫行为控制及植物病害防治中的应用。
  9. 根据权利要求8所述的应用，其特征在于：所述蚜虫行为控制指蚜虫的驱避行为控制；
    所述蚜虫为桃蚜或苹果黄蚜；
    所述植物病害为瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌引起的病害。
  10. 一种蚜虫防治剂、蚜虫行为控制剂或植物病害防治剂，以权利要求1-5中任一项所述的式I-a、式I-b、式I-c所示化合物为活性成分。
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