Jasmonate derivative and application thereof in agriculture

Abstract

The invention discloses a jasmonate derivative and an application thereof in agriculture. According to the jasmonic acid methyl ester derivative, jasmonic acid ester is subjected to cyclopropanation modification, so that the structure of the jasmonic acid ester can be stable. The jasmonate derivative provided by the invention has plant growth regulating activity and bacteriostatic activity, is stable in structure, is nontoxic and harmless to the environment, and can be used as an agricultural bactericide and / or a plant growth regulator.

Description

TECHNICAL FIELD

[0001] The present application relates to a new jasmonate compound, a method for preparing the compound and its use in agriculture. BACKGROUND

[0002] Jasmonic acid (JA) and methyl jasmonate (MeJA) are widely present in plants as a wound-related plant hormone and signal molecule, and exogenous application can stimulate the expression of defense plant genes, induce plant chemical defense, and produce similar effects to mechanical damage and insect feeding. Numerous studies have shown that treatment of plants with jasmonic acid compounds can systematically induce protease inhibitors (PI) and polyphenol oxidase (PPO), thereby affecting the absorption of nutrients by phytophagous animals, and also increasing the activity levels of defense proteins such as peroxidase, chitosanase and lipoxygenase, leading to the accumulation of alkaloids and phenolic secondary metabolites, increasing and changing the release of volatile signal compounds, and even forming defense structures such as trichomes and resin canals. Plants treated with jasmonic acid have increased mortality of phytophagous animals and become more attractive to predatory and parasitic natural enemies. Volatile compounds, methyl jasmonate, can enter the plant body from the stomata of the plant and be hydrolyzed to jasmonic acid in the cytoplasm by esterases, achieving long-distance signal transduction and interplant communication to induce neighboring plants to produce induced defense responses.

[0003] Jasmonic acid and methyl jasmonate have four stereoisomers, of which the cis structure is active, but the cis structure is unstable and can epimerize to the trans structure.

[0004] Patent document CN101001524B reports a salt of dihydrojasmonic acid and its use in agriculture.

[0005] Patent document US13831766 reports jasmonic acid ester derivatives and discloses the use of the compounds in anticancer.

[0006] Patent document CN108569973A discloses a dihydrojasmonic acid (dialkylamino) ester compound or salt thereof, and discloses that the dihydrojasmonic acid (dialkylamino) ester compound has the use of a plant regulator.

[0007] There is still a need in the industry to optimize the stability of jasmonic acid (ester) derivatives and obtain better agricultural use. SUMMARY

[0008] The present application finds that the jasmonic acid ester derivative modified by cyclopropanation can stabilize the structure without affecting the activity, and is non-toxic and harmless, and the modified derivative has new activity and can be used as a new type of plant growth regulator and bacteriostatic agent or fungicide.

[0009] A first aspect of the present application is to provide a compound having the following formula I structure or its optical isomer,

[0010]

[0011] wherein A is -CR1R2-, -NR5-, -O-, or -S-, wherein R1, R2 are independently selected from H, halogen, hydroxyl, C 1-4 alkoxy, C 1-4 alkyl, with the proviso that R1, R2 are not simultaneously H or R1, R2 are not simultaneously Cl;

[0012] R5 is H or C 1-4 alkyl;

[0013] R3 is C 1-4 alkyl or C 2-4 alkenyl;

[0014] R4 is C 1-4 alkyl.

[0015] Preferably, A is -CR1R2- or -NR5-; R1, R2 are independently Cl, Br, F, methyl or methoxy, and R1, R2 are not simultaneously Cl;

[0016] R5 is H, methyl or ethyl;

[0017] R3 is methyl, ethyl, n-propyl, i-propyl, ethenyl or propenyl;

[0018] R4 is methyl, ethyl, n-propyl or i-propyl.

[0019] Preferably, the compound of formula I is selected from:

[0020] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or

[0021] 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0022] A second aspect of the present application is to provide the use of a compound having the following formula I structure or its optical isomer as a plant growth regulator and / or agricultural fungicide and / or agricultural bacteriostat,

[0023]

[0024] wherein A is -CR1R2-, -NR5-, -O-, or -S-, wherein R1, R2 are independently selected from H, halogen, hydroxyl, C 1-4 alkoxy, C 1-4 alkyl;

[0025] R5is H or C 1-4 alkyl;

[0026] R3is C 1-4 alkyl or C 2-4 alkenyl;

[0027] R4is C 1-4 alkyl.

[0028] Preferably, A is -CR1R2- or -NR5-; R1, R2are independently Cl, Br, F, methyl or methoxy;

[0029] R5is H, methyl or ethyl;

[0030] R3is methyl, ethyl, n-propyl, i-propyl, ethenyl or propenyl;

[0031] R4is methyl, ethyl, n-propyl or i-propyl.

[0032] Preferably, the compound of formula I is selected from:

[0033] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0034] 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0035] 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or

[0036] 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0037] More preferably, the compound of formula I is selected from 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0038] According to the present application, the plant growth regulating activity includes, but is not limited to, promoting fruit ripening (e.g. color change or / and increasing sugar content, etc.). In one embodiment of the present application, it can be used to promote fruit ripening of Vitis crops, such as promoting color change or / and increasing sugar content thereof.

[0039] According to the present application, the bacteria are preferably fungi, especially plant pathogenic fungi, such as Botrytis cinerea, Sclerotinia, such as Sclerotinia sclerotiorum, Monilinia, such as Monilinia fructigena, Rhizoctonia, such as Rhizoctonia solani Kühn, Sclerotium, such as Sclerotium rolfsii, and the like. The compounds of formula I according to the present application can kill or inhibit fungi in various forms, including sclerotia, conidia, mycelium and fruiting bodies of fungi, and can be used for preventing and treating plant fungal diseases, such as botrytis, sclerotinia, and the like.

[0040] Therefore, in a preferred technical solution, the use of the compound of formula I or its optical isomer as an agricultural fungicide and / or an agricultural fungistat is provided.

[0041] In some embodiments of the present application, the use of the compound of formula I or its optical isomer in preventing and treating botrytis is provided. The botrytis can be tomato botrytis and the like.

[0042] In some embodiments of the present application, the use of the compound of formula I or its optical isomer in preventing and treating sclerotinia is provided. The sclerotinia can be rape sclerotinia and the like.

[0043] The compound of the present application, when producing the above-mentioned biological effects, will not have a negative impact on the germination, sprout growth and root growth, and root length of plants.

[0044] A third aspect of the present application provides an agricultural composition containing the compound of formula I or its optical isomer,

[0045]

[0046] wherein A is -CR1R2-, -NR5-, -O- or -S-, wherein R1, R2are independently selected from H, halogen, hydroxyl, C 1-4 alkoxy, C 1-4 alkyl; R5is H or C 1-4 alkyl; R3is C 1-4 alkyl or C 2-4 alkenyl; R4is C 1-4 alkyl.

[0047] Preferably, A is -CR1R2- or -NR5-;

[0048] R1, R2are independently Cl, Br, F, methyl or methoxy;

[0049] R5is H, methyl or ethyl;

[0050] R3is methyl, ethyl, n-propyl, i-propyl, ethenyl or propenyl;

[0051] R4is methyl, ethyl, n-propyl or i-propyl.

[0052] Preferably, the compound of formula I in the composition is selected from:

[0053] 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0054] 2-((1 R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0055] 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0056] 2-((1 R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0057] More preferably, the compound of formula I in the composition is selected from 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, 2-((1 R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0058] According to the present application, the agricultural composition can further contain agriculturally acceptable auxiliary ingredients.

[0059] As the biological activity of the aforementioned compound of Formula I, according to the present application, the agricultural composition can be used as a fungistat or fungicide for agricultural fungistasis or fungicidal activity. The fungi are preferably fungi, especially plant pathogenic fungi, such as Botrytis cinerea, Sclerotinia, such as Sclerotinia sclerotiorum, Monilinia, such as Monilinia fructigena, Rhizoctonia, such as Rhizoctonia solani Kühn, Sclerotium, such as Sclerotium rolfsii, and the like. It can be used for the prevention and treatment of plant fungal diseases, such as gray mold (e.g., tomato gray mold), sclerotinia (e.g., rape sclerotinia), and the like.

[0060] According to the present application, the agricultural composition can be used as a plant growth regulator, including but not limited to promoting fruit ripening (e.g., color change or / and increasing sugar content, etc.). In an embodiment of the present application, the agricultural composition is used to promote fruit ripening of Vitis crops, such as promoting color change and / or increasing sugar content.

[0061] According to the present application, the agricultural composition can be used as a fungistat or fungicide for the prevention and treatment of plant fungal diseases, while also being used as a plant growth regulator.

[0062] The present application still further provides a pesticide preparation, which contains the aforementioned agricultural composition, and the pesticide preparation can be in various different dosage forms, such as wettable powder, soluble granules, soluble powder, water dispersible granules, aqueous agent, hot fog agent, ultra-low volume liquid, or microcapsule suspension.

[0063] Different auxiliary ingredients can be selected according to the dosage form of the preparation, including but not limited to water, surfactants, stabilizers known to those skilled in the art, antifreeze agents, fillers, or other ingredients. The surfactants include one or more of dispersants, emulsifiers, wetting agents, thickeners, or antifoaming agents.

[0064] The present application also provides a method for agricultural fungistasis or fungicidal activity, which comprises applying to a plant or its environment a compound having the following Formula I structure or an optical isomer thereof, or an agricultural composition or a pesticide preparation containing the compound or the optical isomer thereof,

[0065]

[0066] wherein A is -CR1R2-, -NR5-, -O-, or -S-, wherein R1, R2are independently selected from H, halogen, hydroxyl, C 1-4 alkoxy, C1-4 alkyl;

[0067] R5is H or C 1-4 alkyl;

[0068] R3is C 1-4 alkyl or C 2-4 alkenyl;

[0069] R4is C 1-4 alkyl.

[0070] Preferably, A is -CR1R2- or -NR5-; R1, R2are independently Cl, Br, F, methyl or methoxy;

[0071] R5is H, methyl or ethyl;

[0072] R3is methyl, ethyl, n-propyl, i-propyl, ethenyl or propenyl;

[0073] R4is methyl, ethyl, n-propyl or i-propyl.

[0074] Preferably, the compound of formula I is selected from:

[0075] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0076] 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0077] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or

[0078] 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0079] More preferably, the compound of formula I is selected from 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0080] The present application also provides a method for regulating the growth of plants, which comprises applying to the plants or their environment a compound having the following formula I structure or an optical isomer thereof or an agricultural composition or a pesticide preparation comprising the compound or the optical isomer thereof,

[0081] wherein A is -CR1R2-, -NR5-, -O- or -S-, wherein R1, R2are independently selected from H, halogen, hydroxy, C 1-4 alkoxy, C 1-4 alkyl;

[0082] R5is H or C 1-4 alkyl;

[0083] R3is C 1-4 alkyl or C 2-4 alkenyl;

[0084] R4is C 1-4 alkyl.

[0085] Preferably, A is -CR1R2- or -NR5-; R1, R2are independently Cl, Br, F, methyl or methoxy;

[0086] R5is H, methyl or ethyl;

[0087] R3is methyl, ethyl, n-propyl, i-propyl, ethenyl or propenyl;

[0088] R4is methyl, ethyl, n-propyl or i-propyl.

[0089] Preferably, the compound of formula I is selected from:

[0090] 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0091] 2-((1 R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0092] 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0093] 2-((1 R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0094] More preferably, the compound of formula I is selected from 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, 2-((1 R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester, or 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0095] The present application also provides a method for inhibiting or killing bacteria and simultaneously regulating plant growth in agriculture, which comprises applying to plants or their environment a compound having the following formula I structure or its optical isomer or an agricultural composition or pesticide preparation comprising the compound or its optical isomer,

[0096] wherein A is -CR1R2-, -NR5-, -O- or -S-, wherein R1, R2 are independently selected from H, halogen, hydroxyl, C 1-4 alkoxy, C 1-4 alkyl;

[0097] R5 is H or C 1-4 alkyl;

[0098] R3 is C 1-4 alkyl or C 2-4 alkenyl;

[0099] R4 is C 1-4 alkyl.

[0100] Preferably, A is -CR1R2- or -NR5-; R1, R2 are independently Cl, Br, F, methyl or methoxy;

[0101] R5 is H, methyl or ethyl;

[0102] R3 is methyl, ethyl, n-propyl, isopropyl, ethenyl or propenyl;

[0103] R4 is methyl, ethyl, n-propyl or isopropyl.

[0104] Preferably, the compound of formula I is selected from:

[0105] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0106] 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0107] 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester,

[0108] 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetic acid methyl ester.

[0109] More preferably, the compound of formula I is selected from methyl 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, methyl 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, or methyl 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate.

[0110] As mentioned above, the agricultural antibacterial or bactericidal method is preferably to inhibit or kill fungi, especially plant pathogenic fungi, such as Botrytis cinerea, Sclerotinia such as Sclerotiniasclerotiorum, Monilinia such as Monilinia fructigena, Rhizoctonia such as Rhizoctonia solaniKühn, Sclerotium such as Sclerotium rolfsii, etc., which are used to prevent and control plant fungal diseases, such as gray mold (such as tomato gray mold), sclerotinia (such as rapeseed sclerotinia), etc.

[0111] The plant growth regulation includes but is not limited to promoting fruit ripening (such as color change and / or increasing sugar content, etc.). In one embodiment of the present invention, it is used to promote fruit ripening of grape crops, such as promoting color change and / or increasing sugar content. DETAILED DESCRIPTION

[0112] The present invention is further described below with reference to the following examples. It should be noted that the examples are not intended to limit the scope of protection of the present invention, and those skilled in the art will understand that any improvements and variations based on the present invention are within the scope of protection of the present invention.

[0113] Glossary and definitions:

[0114] Abscisic acid: commercially available, (S)-5-(1-hydroxy-4-oxo-2,6,6-trimethyl-2-cyclohexen-1-yl)-3-methyl-(2Z,4E)-pentadienoic acid;

[0115] Methyl jasmonate: commercially available, (1R,2R)-3-oxo-2-(2Z)-2-penten-1-ylcyclopentaneacetic acid methyl ester;

[0116] Methyl dihydrojasmonate: commercially available, methyl 2-pentylcyclopentanone-3-acetate;

[0117] ck: control experiment, usually water is used as the control;

[0118] SDS: sodium dodecylsulfate;

[0119] GC: gas chromatography.

[0120] Example 1 Methyl 2-((1 R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3- oxocyclopentyl)acetate

[0121]

[0122] Methyl jasmonate (1.0 g, 4.46 mmol) was dissolved in bromoform (20 ml) and sodium dodecylsulfate (0.05 g, 0.18 mmol) was added. A 50% aqueous solution of sodium hydroxide (20 ml) was added, which was cooled to room temperature. After the addition, the reaction was allowed to react at 80°C for 4 h, and the reaction was monitored by GC. After the reaction was completed, it was cooled to room temperature, and the aqueous phase was extracted with 60 ml of bromoform in three portions. The organic phase was washed with 50 ml of 1 mol / L hydrochloric acid solution and 100 ml of saturated sodium chloride, dried, and concentrated. The compound was separated and purified by column chromatography to obtain a yellow oil (1.18 g, yield 86.5%). The target compound was obtained, which was named as Br-cyclopropane methyl jasmonate in the examples.

[0123] Characterization data: 1 HNMR (300 MHz, DMSO-d6) δ 3.63 (s, 3H), δ 2.55 (m, 2H), δ 2.39 (m, 4H), δ 2.35 (dt, 1H), δ 2.24 (dtd, 1H), δ 1.79 (m, 2H), δ 1.60 (m, 4H), δ 0.95 (td, 3H).

[0124] Example 2 Methyl 2-((1 R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxocyclopentyl)acetate

[0125]

[0126] Methyl jasmonate (1.0 g, 4.46 mmol) was dissolved in an ammonia-methanol solution (7 mol / L 50 ml), and tetrabutylammonium hexafluorophosphate (0.77 g, 2 mmol) was added. A platinum mesh electrode was used as the cathode, and a graphite sheet electrode was used as the anode. After nitrogen was introduced for protection, a current of 3 Ma / cm2was applied under water bath conditions for 4 h. The reaction was monitored by GC. After the reaction was completed, it was cooled to room temperature, and the aqueous phase was extracted with 60 ml of bromoform in three portions. The organic phase was washed with 50 ml of 1 mol / L hydrochloric acid solution and 100 ml of saturated sodium chloride, dried, and concentrated. The compound was separated and purified by column chromatography to obtain a yellow oil (1.18 g, yield 86.5%). The target compound was obtained, which was named as Br-cyclopropane methyl jasmonate in the examples. 2The electrolysis was carried out under constant current, and the reaction was detected by GC. After the reaction was completed, 100 ml of 1 mol / L hydrochloric acid solution was added, and 300 ml of dichloromethane was extracted three times. The organic phase was washed with 50 ml of 1 mol / L sodium hydroxide solution, dried and concentrated, and then separated and purified by a chromatographic column to obtain an oily compound (0.69 g, yield 64.7%). The target compound was obtained, which was named as N-heterocyclic jasmonic acid methyl ester in the application example.

[0127] Characterization data: 1 HNMR (300 MHz, DMSO-d6) δ 3.64 (S, 3H), δ 2.82 (m, 2H), δ 2.57 (m, 1H) δ 2.47 (dt, 1H), δ 2.37 (m, 4H) δ 1.88 (ddt, 1H), δ 1.80 (ddd, 1H), δ 1.69 (ddd, 1H) δ 1.65 (m, 1H), δ 1.62 (m, 1H), δ 1.55 (m, 1H), δ 1.46 (m, 1H) δ 0.89 (td, 3H)

[0128] Example 3 Methyl 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo- cyclopentyl)acetate

[0129]

[0130] Methyl jasmonate (1.0 g, 4.46 mmol) was dissolved in chloroform (20 ml), and sodium dodecyl sulfate (0.05 g, 0.18 mmol) was added. Then 50% sodium hydroxide aqueous solution (20 ml) cooled to room temperature was added, and after the addition was completed, the reaction solution was reacted at 80°C for 4 h, and the reaction was detected by GC. After the reaction was completed, it was cooled to room temperature, separated, and the aqueous phase was extracted with 60 ml of chloroform three times. The organic phase was washed with 50 ml of 1 mol / L hydrochloric acid solution, 100 ml of saturated sodium chloride, dried and concentrated, and then separated and purified by a chromatographic column to obtain a yellow oily compound (1.18 g, yield 86.5%). The target compound was obtained, which was named as Cl-cyclopropane methyl jasmonate in the application example.

[0131] Characterization data: 1 HNMR (300 MHz, DMSO-d6) δ 3.63 (s, 3H), δ 2.57 (m, 2H), δ 2.37 (m, 4H), δ 2.18 (dt, 1H), δ 2.01 (dtd, 1H), δ 1.84 (m, 2H), δ 1.58 (m, 4H), δ 0.96 (td, 3H)

[0132] Biological activity test

[0133] Example 4 Grape color change experiment

[0134] Drug concentration: The color-changing preparation described in the present application, the test solution is prepared, the amount of abscisic acid treatment is 2 ppm, the amount of methyl jasmonate modifier is 2 ppm. The experiment is divided into 1 control and 4 treatments, respectively: water treatment (ck); abscisic acid; Br-cyclopropane methyl jasmonate; N heterocyclic methyl jasmonate; Cl-cyclopropane methyl jasmonate.

[0135] Experimental method: When the summer black grape just enters the color-changing period, evenly and fully spray the fruit, each single plant is a small area, and 3 repeats are set. The control takes the same group of drip irrigation, the same greenhouse, and ensures that the conditions such as water and fertilizer are basically the same.

[0136] Application method: The first spraying treatment is carried out 18 days before picking (the grape has been colored for 20%), the second spraying treatment is carried out 7 days later, the third spraying treatment is carried out 14 days later, 3 repeats, 5 grapevines per repeat.

[0137] Fruits are picked from the upper and lower parts of the same grape cluster, 10 uniform and undamaged fruits are selected as a group, each part is random, each plant is random, and three groups are taken. The collected fruits are washed with clean water, dried, the soluble solids content is measured with a sugar meter, and the data is recorded.

[0138] Select whole grape clusters for color index evaluation, and the color index evaluation criteria are as follows:

[0139] I. About 20% or less of the whole grape cluster is colored

[0140] II. About 20-40% of the whole grape cluster is colored

[0141] III. About 40-60% of the whole grape cluster is colored

[0142] IV. About 60-80% of the whole grape cluster is colored

[0143] V. About 80% or more of the whole grape cluster

[0144] The experimental data results are shown in Table 1, in which top sugar is the test result of the upper part sample, and bottom sugar is the test result of the lower part sample.

[0145] Table 1 Grape color-changing experiment data

[0146]

[0147]

[0148] 1. The test results show that Br-cyclopropane methyl jasmonate, N heterocyclic methyl jasmonate, and Cl-cyclopropane methyl jasmonate have obvious sugar-increasing effect on summer black grape.

[0149] 2. After the treatment of the jasmonate derivatives of the present application, the coloring time of the grapes is significantly shortened, and 60-80% of the grapes can be colored after 7 days of treatment, which shows that the jasmonate derivatives of the present application have a color-enhancing effect.

[0150] Example 5 Bacteriostatic experiment

[0151] Drug concentration: 10000 ppm methyl jasmonate, Br-cyclopropane methyl jasmonate, N-heterocyclic methyl jasmonate and Cl-cyclopropane methyl jasmonate were respectively configured.

[0152] Experimental method: In the clean bench, the prepared drug solution was added to the PDA medium after sterilization at about 50°C, and mixed thoroughly to prepare the drug-containing PDA plate with a final concentration of 50 mg / L. The PDA plate without drug was used as a blank control, and each treatment was repeated 3 times. After the medium was solidified, a 7 mm diameter punch was used to take a bacterial cake from the edge of the activated test bacteria plate, and the mycelium was inoculated in the center of the drug-containing plate with the mycelium facing down. Press gently to make it adhere to the surface of the medium. Cover the culture dish cover and invert it in a 25°C incubator in the dark. When the colony diameter of the blank control grows to 5-6 cm, the colony diameter of each treatment group is measured by cross method, and the mycelial growth inhibition rate of the cyclopropane methyl jasmonate compound on the test fungus is calculated.

[0153] The mycelial growth inhibition rate is calculated as follows:

[0154] Inhibition rate (%) = (Dc-Dt) / Dc x 100

[0155] In the formula, Dc is the average diameter of the control group (mm), and Dt is the average diameter of the drug treatment group (mm).

[0156] Table 2 Bacteriostatic experiment results

[0157]

[0158]

[0159] Compared with methyl jasmonate, Br-cyclopropane methyl jasmonate, N-heterocyclic methyl jasmonate and Cl-cyclopropane methyl jasmonate have obvious bacteriostatic effect on Sclerotinia sclerotiorum and Botrytis cinerea.

[0160] Example 6 Environmental impact experiment-wheat seed germination

[0161] Test method: Select the same size, full grain wheat seeds, first with sodium hypochlorite (concentration of 2.5%) disinfection 15 min, then with distilled water to clean the seeds, and then the seeds in the treatment solution for 8h. After soaking in the culture dish with two layers of filter paper, the grain abdominal groove is evenly placed downward, and the culture dish is placed in a (25±1)℃ incubator, and germination is carried out in the dark.

[0162] Distilled water is added to the culture dish every day to keep the filter paper wet, and the seed germination condition is observed. The germination rate, bud length and root length are measured on the 6th day, and the data is recorded.

[0163] Experimental group setting: set up one control group and six experimental groups. The treatment concentration is: abscisic acid 20mg / L, methyl jasmonate 20mg / L, Br-cyclopropane methyl jasmonate 20mg / L, N heterocyclic methyl jasmonate 20mg / L, Cl-cyclopropane methyl jasmonate 20mg / L, dihydro methyl jasmonate 20mg / L. Each group has 50 seeds, and three replicates are set.

[0164] The test results are shown in Tables 3-5. The test results show that Br-cyclopropane methyl jasmonate, N heterocyclic methyl jasmonate and Cl-cyclopropane methyl jasmonate do not have a negative effect on the germination rate, bud length and root length of wheat seeds.

[0165] Table 3 Wheat seed germination rate treated with different agents

[0166]

[0167] Table 4 Average bud length of wheat seed germination treated with different agents

[0168]

[0169] Table 5 Average root length of wheat seed germination treated with different agents

[0170]

[0171] The above describes embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A compound having the structure of formula I or an optical isomer thereof, in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy, C 1-4 Alkyl, provided that R1 and R2 are not H at the same time or R1 and R2 are not Cl at the same time; R5 is H or C 1-4 alkyl; R3 is C 1-4 Alkyl or C 2-4 alkenyl; R4 is C 1-4 alkyl; Preferably, wherein A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy, and R1 and R2 are not Cl at the same time; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or Methyl 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate.

2. Use of a compound having the structure of the following formula I or an optical isomer thereof as a plant growth regulator and / or agricultural fungicide and / or agricultural bacteriostat: in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy, C 1-4 Alkyl; R5 is H or C 1-4 Alkyl; R3 is C 1-4 Alkyl or C 2-4 Alkenyl; R4 is C 1-4 alkyl; Preferably, A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound of formula I is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or Methyl 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate.

3. The use according to claim 2, wherein the plant growth regulation is to promote fruit ripening; preferably, to promote fruit ripening of grape plants; preferably, to promote color change and / or increase sugar content of grape plant fruits.

4. The use according to claim 2, wherein the fungus is a plant pathogenic fungus, preferably Botrytis cinerea, Sclerotinia such as Sclerotinia sclerotiorum, Monilinia such as Monilinia fructigena, Rhizoctonia such as Rhizoctonia solani Kühn, or Sclerotium such as Sclerotium rolfsii. Preferably, the use is to control gray mold and / or sclerotinia.

5. An agricultural composition comprising a compound of the following formula I or an optical isomer thereof: in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy, C 1-4 Alkyl; R5 is H or C 1-4 Alkyl; R3 is C 1-4 Alkyl or C 2-4 Alkenyl; R4 is C 1-4 alkyl; Preferably, in Formula I, A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound of formula I is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or Methyl 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate.

6. The agricultural composition according to claim 5, wherein The composition further contains agriculturally acceptable adjunct ingredients.

7. A pesticide formulation comprising the composition according to claim 5 or 6; preferably, the formulation is in the form of a wettable powder, a soluble granule, a soluble powder, a water-dispersible granule, an aqueous solution, a thermal mist, an ultra-low volume liquid, or a microcapsule suspension.

8. A method for inhibiting or sterilizing fungi in agriculture, comprising applying a compound having the structure of the following formula I or an optical isomer thereof, or the agricultural composition according to claim 5 or 6, or the pesticide formulation according to claim 7 to a plant or its environment: in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy, C 1-4 Alkyl; R5 is H or C 1-4 Alkyl; R3 is C 1-4 Alkyl or C 2-4 Alkenyl; R4 is C 1-4 alkyl; Preferably, A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound of formula I is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate; Preferably, the agricultural bacteriostasis or bactericidal agent is to inhibit or kill plant pathogenic fungi; preferably, the plant pathogenic fungi are selected from Botrytis cinerea, Sclerotinia such as Sclerotiniasclerotiorum, Monilinia such as Monilinia fructigena, Rhizoctonia such as Rhizoctonia solaniKühn, Sclerotium such as Sclerotium rolfsii; Preferably, the agricultural bacteriostasis or sterilization is to prevent and control gray mold and / or sclerotinia disease.

9. A method for regulating plant growth, comprising applying to the plant or its environment a compound having the structure of the following formula I or an optical isomer thereof, or the agricultural composition according to claim 5 or 6, or the pesticide formulation according to claim 7, in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy, C 1-4 Alkyl; R5 is H or C 1-4 Alkyl; R3 is C 1-4 Alkyl or C 2-4 Alkenyl; R4 is C 1-4 alkyl; Preferably, A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound of formula I is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate; Preferably, the regulating plant growth is promoting fruit ripening; Preferably, the regulating plant growth is promoting fruit ripening of grape crops; Preferably, the regulating plant growth is promoting color change and / or increasing sugar content of grape fruit.

10. A method for inhibiting or killing bacteria in agriculture and regulating plant growth, the method comprising applying a compound having the structure of the following formula I or its optical isomer, or the agricultural composition according to claim 5 or 6, or the pesticide formulation according to claim 7 to a plant or its environment: in, A is -CR1R2-, -NR5-, -O- or -S-, wherein R1 and R2 are independently selected from H, halogen, hydroxyl, C 1-4 Alkoxy or C 1-4 Alkyl; R5 is H or C 1-4 Alkyl; R3 is C 1-4 Alkyl or C 2-4 Alkenyl; R4 is C 1-4 alkyl; Preferably, A is -CR1R2- or -NR5-; R1 and R2 are independently Cl, Br, F, methyl or methoxy; R5 is H, methyl or ethyl; R3 is methyl, ethyl, n-propyl, isopropyl, vinyl or propenyl; R4 is methyl, ethyl, n-propyl or isopropyl; Preferably, the compound of formula I is selected from: 2-((1R,2R)-2-((2,2-dibromo-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((3-ethylaziridine-2-)methyl)-3-oxo-cyclopentane)acetate, 2-((1R,2R)-2-((2,2-dichloro-3-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate, or Methyl 2-((1R,2R)-2-((2-ethylcyclopropane)methyl)-3-oxo-cyclopentane)acetate.

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