Aspergillus terreus ketone ester derivative as well as preparation method and application thereof

Abstract

The invention relates to the technical field of green agriculture, in particular to an aspergillus terreus ketone ester derivative as well as a preparation method and application thereof. The structural formula of the terreus ketone ester derivative is as shown in a formula 1, wherein the structure of R1 in the structural formula 1 comprises at least one of hydrogen, C1-3 alkyl, C2-3 alkenyl, C2-3 alkynyl, C1-3 alkoxy, C3-5 cycloalkyl, C3-5 cycloalkyloxy, halogen, nitryl, cyano, trifluoromethyl, 3-7-membered heterocyclic radical, C6-10 aryl and C6-10 heteroaryl. The prevention and control effect of the aspergillus terreus ketone ester derivative is remarkably improved, the solubility is increased, the weed prevention and control spectrum is expanded, and the aspergillus terreus ketone ester derivative has the potential of being developed into a microbial herbicide.

Description

Technical Field

[0001] This invention relates to the field of green agricultural technology, specifically to a terbinazone derivative, its preparation method, and its application. Background Technology

[0002] Natural products are an important molecular treasure trove of potential lead drugs. In the past decade, among the new drugs approved by the FDA, 28 entities were based on natural products or semi-synthetic derivatives of natural products, accounting for 8.5% of the total number of new drugs approved by the FDA (331 cases). At the same time, compared with molecules synthesized by traditional chemicals, natural products have rich skeletal diversity and structural complexity, demonstrating a huge advantage in new drug creation.

[0003] However, complex natural products also face numerous bottlenecks in actual industrial production. For example, most natural drugs suffer from low content, complex separation and purification processes, and extreme difficulty in total chemical synthesis. The high production costs severely restrict the practical application of natural products, leading the pharmaceutical industry to reduce its motivation for research and development of natural products since the 1990s. In recent years, with the continuous development of science and technology, these difficulties are gradually being resolved, and new opportunities are being discovered. The industrial total synthesis of more and more complex natural products has been achieved, such as ilacycline and orlistat, marking the rise of a research boom using natural products as lead compounds.

[0004] Previous studies have found that terbufotoxin has a simple fermentation process, abundant content (reaching 0.3~0.5 g / L in the fermentation product of PDW), easy separation and purification, and a simple and clear chemical molecular structure, making it a microbial herbicide precursor with great research value. However, it is undeniable that its herbicidal and other biological activities are not outstanding enough, its herbicidal effect is not strong, its solubility is moderate, and its control spectrum is narrow (mainly concentrated on dicotyledonous amaranth weeds). Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention enhances the biological activity of terbufoten through chemical modification, thereby increasing its practical application value. The terbufoten ester derivatives developed in this study exhibit significantly improved control efficacy, increased solubility, and a broader spectrum of weed control, demonstrating the potential to be developed into microbial herbicides. The specific details of this invention are as follows: In a first aspect, the present invention provides a terbinazone derivative, the structural formula of which is shown in Formula 1:

[0006] In the aforementioned structural formula 1, the structure of R1 includes hydrogen and C. 1-3 Alkyl, C 2-3 alkenyl, C 2-3 alkynyl group, C1-3 Alkoxy, C 3-5 cycloalkyl, C 3-5 Cycloalkyloxy, halogen, nitro, cyano, trifluoromethyl, 3-7 membered heterocyclic groups, C 6-10 Aryl, C 6-10 At least one of the aromatic compounds.

[0007] Further, the C6-10 aryl group or C6-10 aryl heterol group is an unsubstituted or R2-substituted C6-10 aryl group or C6-10 aryl heterol group, wherein: R2 is a halogen, C 1-3 At least one of alkoxy, difluoromethyl, and trifluoromethyl.

[0008] Furthermore, R1 includes: , , , , , , , , , , , , , , , , , , At least one of ClCH2- and BrCH2-.

[0009] Furthermore, the terbinazone derivative is selected from at least one of the following: .

[0010] In a second aspect, the present invention provides a method for preparing the aforementioned terbinazone derivatives, the method comprising the following steps: Using anhydrous dichloromethane as the reaction solvent, at least one of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl), dicyclohexylcarbodiimide (DCC), and diisopropylcarbodiimide (DIC) as the condensing agent, and 4-dimethylaminopyridine as the catalyst, terbinafine is reacted with different substrate carboxylic acids to obtain the terbinafine ester derivatives.

[0011] Furthermore, the structural formulas of the different substrate carboxylic acids are shown in Formula 2:

[0012] In the aforementioned structural formula 2, the structure of R1 includes hydrogen and C.1-3 Alkyl, C 2-3 alkenyl, C 2-3 alkynyl group, C 1-3 Alkoxy, C 3-5 cycloalkyl, C 3-5 Cycloalkyloxy, halogen, nitro, cyano, trifluoromethyl, 3-7 membered heterocyclic groups, C 6-10 Aryl, C 6-10 At least one of the aromatic compounds.

[0013] Furthermore, the C 6-10 Aryl, C 6-10 The aromatic heterol group is an unsubstituted or R2-substituted C 6-10 Aryl, C 6-10 Aromatic heteroyl groups, wherein: R2 is a halogen, C 1-3 At least one of alkoxy, trifluoromethyl, nitro, and cyano.

[0014] Furthermore, R1 includes: , , , , , , , , , , , , , , , , , , At least one of ClCH2- and BrCH2-.

[0015] Furthermore, the method also includes a step of separating and purifying the obtained terbinazone derivative.

[0016] Furthermore, the steps for separating and purifying the terbinazone derivatives specifically include the following operations: The fully reacted terbinazone derivatives are quenched with a high-concentration salt reagent and then separated and purified by liquid-liquid extraction. Optionally, the liquid-liquid extraction method specifically includes extraction with an organic solvent followed by washing with an inorganic salt solution to obtain the target product.

[0017] Optionally, a saturated sodium chloride solution is used for quenching the reaction; the organic solvent used for liquid-liquid extraction includes at least one of ethyl acetate, dichloromethane, diethyl ether, and chloroform, and the inorganic salt solution used for liquid-liquid extraction includes at least one of sodium carbonate and sodium bicarbonate solutions.

[0018] In a specific embodiment of the present invention, the step of separating and purifying the terbinazone derivative is as follows: After the reaction was complete, the reaction was quenched with saturated sodium chloride solution, extracted with ethyl acetate, the organic phase was washed with saturated NaHCO3 water, the organic phases were combined, concentrated and dried, and the target product was obtained by column chromatography.

[0019] Furthermore, the method further includes a step of preparing terbinazone. Optionally, the step of preparing terbinazone involves fermenting and culturing Aspergillus terbinazone strains followed by isolation and purification to obtain the terbinazone compound.

[0020] In one embodiment of the present invention, the steps for preparing terbinafine specifically include the following operations: Aspergillus terreus was obtained by fermenting Aspergillus with accession number CGMCC No. 20251, filtering the fermentation broth, and then extracting the active ingredient.

[0021] In a third aspect, the present invention provides a composition comprising at least the aspergillus ester derivatives described herein and agriculturally acceptable additives.

[0022] Optionally, the additive includes at least one of the following synergists whose main components are methyl oleate, isomeric alcohol ether, and lauric acid-diisopropanolamine (LA-DIPA).

[0023] In a fourth aspect, the present invention provides the use of the aforementioned terbinafine ester derivatives, the method thereof, or the composition thereof in the preparation of herbicidal products.

[0024] Furthermore, the herbicides include at least one of the genera Amaranth, Euphorbia, Euphorbia, and Lorula.

[0025] The beneficial effects of the present invention include, but are not limited to: This invention utilizes anhydrous dichloromethane as the reaction solvent, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride as the condensing agent, and 4-dimethylaminopyridine as the catalyst to react terbinafine with different substrate carboxylic acids to obtain the aforementioned terbinafine ester derivatives. The preparation method is simple, requiring only one step to obtain the terbinafine ester derivatives.

[0026] Aspergillus terrestris ester derivatives show significantly improved control efficacy, increased solubility, and a broader spectrum of weed control, and have the potential to be developed into microbial herbicides. Attached Figure Description

[0027] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a synthetic route diagram of compounds II-1 to II-22 in Example 2 of the present invention.

[0028] Figure 2 This is a schematic diagram showing the results of compounds II-16, II-17, and II-18 inhibiting the growth of Amaranthus retroflexus in Example 3 of this invention.

[0029] Figure 3 This is a schematic diagram showing the results of compounds II-16, II-17, and II-18 inhibiting the growth of ryegrass in Example 3 of the present invention.

[0030] Figure 4 This is a schematic diagram showing the results of compounds II-16, II-17, and II-18 inhibiting the growth of cat's eye grass in Example 3 of the present invention.

[0031] Figure 5 This is a graph showing the excellent inhibitory effects of compounds II-21 and II-22 in Example 3 of this invention on *Amaranthus retroflexus*, *Heliotropium indicum*, *Eriocaulon buergerianum*, and *Leraria lobata* at a concentration of 1 mM. In the graph, a represents *Amaranthus retroflexus*; b represents *Heliotropium indicum*; c represents *Eriocaulon buergerianum*; and d represents *Leraria lobata*.

[0032] Figure 6 This is a graph showing the inhibition of the radicle and plumule of Amaranthus retroflexus at different concentrations of II-21 and II-22 in Example 3 of the present invention.

[0033] Figure 7 The EC values ​​of the reverse-branch amaranth radicles in Examples 3 of this invention are II-9, II-21, and II-22. 50 picture.

[0034] Figure 8 The EC values ​​of the anti-branching amaranth embryos II-9, II-21, and II-22 in Embodiment 3 of this invention are... 50 picture.

[0035] Figure 9 This is a graph showing the inhibition of cat's eye grass radicles and plumules by different concentrations of II-16, II-17, and II-18 in Example 3 of the present invention.

[0036] Figure 10 This is a graph showing the inhibition of cat's eye grass radicles and plumules by II-21 and II-22 at different concentrations in Example 3 of the present invention.

[0037] Figure 11The EC values ​​of cat's-eye grass radicles in Examples 3 of this invention are II-21 and II-22. 50 picture.

[0038] Figure 12 The EC values ​​of cat's-eye grass embryos II-16, II-17, II-18, II-21, and II-22 in Embodiment 3 of this invention are... 50 picture. Detailed Implementation

[0039] The present invention is described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments. Unless otherwise specified, the raw materials and catalysts in the embodiments of the present invention are all purchased through commercial channels.

[0040] strain source: Aspergillus from the rhizosphere soil of mangroves in Hainan Aspergillus sp. HT5 has been deposited at the China General Microbiological Culture Collection Center (CGMCC) with accession number CGMCC No. 20251 and a deposit date of August 31, 2020. This strain has been disclosed in Chinese patent CN116515637A.

[0041] Example 1: Extraction of Aspergillus terrestris The strain was cultured on potato dextrose agar (PDA) for one week, and then a piece of mycelial cake (d = 5 mm) was transferred to potato dextrose water (PDW) agar and cultured at 28°C and 180 rpm for 72 h to obtain seed culture. 200 mL of PDW medium was prepared in a 500 mL fermentation flask, autoclaved at 121°C for 20 min, and then 5 mL of seed culture was added. The culture was then incubated at 28°C and 180 rpm for 14 days, yielding a total of 55 L of fermentation broth.

[0042] Potato glucose agar (PDA) medium: 6 g / L potato extract powder, 20 g / L glucose, 20 g / L agar, and the remainder is deionized water.

[0043] Potato glucose aqueous culture medium: 6 g / L potato extract powder, 20 g / L glucose, and the remainder is deionized water.

[0044] After fermentation, the bacterial solution and bacterial cells were filtered and separated using gauze. The bacterial solution was extracted three times with twice its volume of ethyl acetate. The bacterial cells were extracted with methanol:dichloromethane (1:1), then evaporated to dryness under reduced pressure. The remaining aqueous solution after solvent evaporation was extracted three times with an equal volume of ethyl acetate. Finally, the ethyl acetate extracts of the bacterial solution and bacterial cells were mixed and evaporated to dryness under reduced pressure to obtain the fermentation extract.

[0045] The above fermentation extract was separated and recrystallized using normal-phase reduced-pressure column chromatography to obtain terbinafine raw material. (For specific procedures, please refer to paragraphs [0063-0068] of the specification of Chinese Invention Patent CN116515637A).

[0046] Example 2 Synthesis of Aspergillus terrestris ester compounds The synthetic routes for terbinazone esters are shown below. Figure 1 .

[0047] (1) Synthesis of (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diethylidene (2-(4-bromophenoxy)acetic acid) (compound II-18).

[0048] Take a 100 mL round-bottom flask and dissolve terbufotoxin (100 mg, 0.65 mmol, 1 eq.) in 10 mL of anhydrous DCM at 25 °C. Then, slowly add DMAP (63.5 mg, 0.52 mmol, 0.8 eq.) and EDCl (373.8 mg, 1.95 mmol, 3 eq.), and stir for 10 min. Then, dissolve p-bromophenoxyacetic acid (330.3 mg, 1.43 mmol, 2.2 eq.) in 5 mL of anhydrous DCM and add it dropwise to the above mixture. Stir at 25 °C for 6 h. Monitor the reaction progress by TLC. After the reaction is complete, wash the mixture three times with saturated NaCl, add ethyl acetate, separate the aqueous phase, and wash the organic layer three times with NaHCO3. Combine the organic layers and dry and concentrate. The target product II-18 (233.7 mg, 62%) was obtained by column chromatography with petroleum ether:ethyl acetate (V1:V2=2:1) ​​as the eluent.

[0049] II-18 1 H NMR (400 MHz, Chloroform- d ) δ 7.36 (dd, J = 9.1, 2.7 Hz, 4H), 6.81– 6.75 (m, 4H), 6.43 – 6.32 (m, 1H), 6.30 (d, J = 16.3 Hz, 1H), 6.23 (s, 1H), 6.17 (d, J = 2.4 Hz, 1H), 5.39 (d, J = 2.6 Hz, 1H), 4.80 – 4.65 (m, 4H), 1.90(d, J= 6.2 Hz, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 195.24, 168.50, 168.45, 164.43,156.74, 156.65, 141.27, 132.62, 132.55, 128.47, 124.20, 116.57, 116.38,114.46,114.33,78.42, 75.46, 65.18, 65.01,29.82, 19.73. (2) Synthesis of (1R,2S)-5-oxo-3-((E)-1-propenyl)cyclopent-3-ene-1,2-dimethylbis(3,4,5-trimethoxybenzoate) (compound II-20).

[0050] Take a 100 mL round-bottom flask and dissolve terbufotoxin (100 mg, 0.65 mmol, 1 eq.) in 10 mL of anhydrous DCM at 25 °C. Then, slowly add DMAP (63.5 mg, 0.52 mmol, 0.8 eq.) and EDCI (373.8 mg, 1.95 mmol, 3 eq.), and stir for 10 min. Then, dissolve 3,4,5-trimethoxybenzoic acid (303.4 mg, 1.43 mmol, 2.2 eq.) in 5 mL of anhydrous DCM and add it dropwise to the above mixture. Stir at 25 °C for 6 h. Monitor the reaction progress by TLC. After the reaction is complete, wash the mixture three times with saturated NaCl, add ethyl acetate, separate the aqueous phase, and wash the organic layer three times with NaHCO3. Combine the organic layers and dry and concentrate. The target product II-20 (303 mg, 86%) was obtained by column chromatography with petroleum ether:ethyl acetate (V1:V2=10:1) as the eluent.

[0051]

[0052] 1 H NMR (600 MHz, Chloroform- d) δ 7.34 (s, 2H), 7.31 (s, 2H), 6.51 (s,1H), 6.50 – 6.46 (m, 1H), 6.43 (d, J = 16.2 Hz, 1H), 6.35 (s, 1H), 5.53 (d, J= 2.5 Hz, 1H), 3.92 (d, J = 9.1 Hz, 12H), 3.90 (s, 6H), 1.92 (d, J = 6.2 Hz, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 196.91, 165.47, 165.34, 165.03,153.08, 152.92, 142.87, 142.68, 140.60, 128.50, 124.65, 123.81, 123.80,107.33, 107.18, 79.11, 77.05, 75.34, 60.98, 60.95, 56.31, 56.25, 19.64. (3) Synthesis of (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-di(2-chloroacetic acid) (compound II-21) Take a 100 mL two-necked flask, connect an external three-way valve to an N2 balloon, and dissolve terbufotoxin (100 mg, 0.65 mmol, 1 eq.) in 10 mL of anhydrous DCM at 0 °C. Then slowly add DMAP (63.5 mg, 0.52 mmol, 0.8 eq.) and EDCI (373.8 mg, 1.95 mmol, 3 eq.), stirring for 10 min while mixing. Immediately afterward, use an external water pump to evacuate the air three times. Then add chloroacetyl chloride (113.8 mg, 0.8 eq.). u L (1.43 mmol, 2.2 eq.) was dissolved in 5 mL of anhydrous DCM and slowly added dropwise to the above mixture. The mixture was stirred at 25 °C for 6 h. The reaction progress was monitored by TLC. After the reaction was completed, the mixture was washed three times with saturated NaCl, ethyl acetate was added, the aqueous phase was separated, and the organic layer was washed three times with NaHCO3. The organic layers were combined, dried, and concentrated. The product II-21 (89.7 mg, 45%) was obtained by column chromatography with dichloromethane:methanol (V1:V2 = 100:1) as the eluent. The reaction ratios and experimental procedures for other compounds were kept consistent.

[0053]

[0054] 1 H NMR (500 MHz, Chloroform- d ) δ 6.47 – 6.38 (m, 1H), 6.33 (d, J =15.0 Hz, 1H), 6.24 (s, 1H), 6.13 (d, J = 5.0 Hz, 1H), 5.33 (d, J = 5.0 Hz, 1H), 4.19 (d, J = 3.6 Hz, 2H), 4.14 (s,1H), 1.96 (d, J = 5.0 Hz, 3H). 13 C NMR (151 MHz, Chloroform- d ) δ 195.04, 166.96, 166.90, 164.36,141.49, 128.50, 124.13, 79.03, 76.16, 40.52, 40.46, 19.68. (4) Preparation of other compounds By replacing R1 in (1)-(3) with different R1 groups in Table 1, and using 1.43 mmol in each case, the experimental steps were repeated to obtain a series of terbinazone ester derivatives. These compounds were all derived by introducing aryl carboxylic acids into terbinazone and their chemical structures and physicochemical properties are shown in Table 1.

[0055] Table 1. Structure and physicochemical properties of Aspergillus terrestris ester derivatives

[0056] Characterization of the target compound:

[0057] (1R,2S)-5-oxo-3-((E)-1-propenyl)cyclopent-3-ene-1,2-diol bis(3-methylthiophene-2-carboxylate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(3-methylthiophene-2-carboxylate) 1 H NMR (400 MHz, Chloroform- d) δ 7.43 (dd, J = 7.9, 5.0 Hz, 2H), 6.92(dd, J = 11.3, 5.0 Hz, 2H), 6.55 – 6.44 (m, 1H), 6.42 (d, J = 9.9 Hz, 1H), 6.39(d, J = 2.4 Hz, 1H), 6.28 (s, 1H), 5.45 (d, J = 2.6 Hz, 1H), 2.53 (s, 6H), 1.90(d, J = 6.3 Hz, 3H).

[0058] 13 C NMR (151 MHz, Chloroform- d ) δ 196.92, 164.90, 161.65, 161.59,147.73, 147.71, 140.67, 131.97, 131.72, 131.29, 131.16, 128.25, 125.21,124.52, 78.78, 74.96, 19.58, 16.13, 16.11.

[0059] HR-ESI-MS (m / z 403.0669 [M+H]) + , Cal. 402.4790).

[0060]

[0061] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(2-methylfuran-3-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(2-methylfuran-3-carboxylate) 1 H NMR (400 MHz, Chloroform- d ) δ 7.24 (d, J = 2.0 Hz, 1H), 7.21 (d, J =2.0 Hz, 1H), 6.65 (d, J= 2.0 Hz, 1H), 6.63 (d, J = 4.0 Hz, 1H), 6.51 – 6.41(m, 1H), 6.39 (d, J =7.0 Hz, 1H), 6.36 (d, J = 2.2 Hz, 1H), 6.27 (s, 1H), 5.39(d, J = 2.6 Hz, 1H), 2.55 (s, 6H), 1.90 (d, J = 4.0 Hz, 3H).

[0062] 13 C NMR (151 MHz, Chloroform- d ) δ 197.40, 165.23, 162.99, 162.94,160.56, 160.46, 140.70, 140.58, 140.48, 128.15, 124.57, 112.41, 112.34,110.82, 110.65, 78.52, 74.46,19.57,13.95.

[0063] HR-ESI-MS (m / z 371.1126 [M+H]) + , Cal.370.3570).

[0064]

[0065] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-dimethylbis(5-methylisoxazole-3-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(5-methylisoxazole-3-carboxylate) 1 H NMR (600 MHz, Chloroform- d ) δ 6.52 – 6.47 (m, 1H), 6.45 (s, 2H), 6.44 (d, J = 2.4 Hz, 1H), 6.40 (d, J = 18.0 Hz, 1H), 6.31 (s, 1H), 5.64 (d, J=6.0 Hz, 1H), 2.51 (d, J = 6.0 Hz, 6H), 1.93 (d, J = 6.0 Hz, 3H).

[0066] 13 C NMR (151 MHz, Chloroform- d ) δ 194.91, 171.90, 164.27, 159.23,155.36 (d, J = 7.0 Hz), 141.10, 128.71, 124.32, 102.61 (d, J = 7.7 Hz), 78.66,76.00, 29.71, 19.64, 12.36 (d, J = 4.8 Hz).

[0067]

[0068] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(3,5-dimethylbenzoate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(3,5-dimethylbenzoate) 1 H NMR (600 MHz, Chloroform-d) δ 7.68 (d, J = 9.7 Hz, 4H), 7.22 (s,1H), 7.19 (s, 1H), 6.50 (d, J = 2.4 Hz, 1H), 6.49 – 6.44 (m, 1H), 6.41 (d, J= 16.3 Hz, 1H), 6.32 (s, 1H), 5.55 (d, J = 2.5 Hz, 1H), 2.35 (d, J = 13.6 Hz, 13H), 1.89 (d, J = 6.3 Hz, 3H).

[0069] 13C NMR (151 MHz, Chloroform-d) δ 197.16, 166.07, 165.99, 165.31,140.45, 138.29, 138.01, 135.31, 135.11, 128.93, 128.85, 128.36, 127.83,127.68, 124.63, 78.79, 75.12, 21.14, 21.11, 19.56.

[0070]

[0071] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(5-methoxypyrazine-2-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(5-methoxypyrazine-2-carboxylate) 1 H NMR (400 MHz, Chloroform- d ) δ 8.89 (dd, J = 8.0, 4.0 Hz, 2H), 8.28(dd, J = 4.0, 1.1 Hz, 2H), 6.58 (d, J =4.0 Hz, 1H), 6.55 – 6.44 (m, 1H), 6.42(d, J = 16.2 Hz,1H), 6.32 (s, 1H), 5.70 (d, J = 2.6 Hz, 1H), 4.05 (s, 3H), 4.04(s, 3H), 1.89 (d, J = 8.0 Hz, 3H).

[0072] 13 C NMR (151 MHz, Chloroform- d) δ 195.91, 164.70, 163.44, 163.32,162.39, 162.29, 144.94, 144.85, 140.83, 135.98, 135.75, 134.60, 134.58,128.65, 124.54, 79.00, 75.74, 54.60, 54.54, 19.64.

[0073]

[0074] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylate) 1 H NMR (500 MHz, Chloroform- d ) δ 7.95 (s, 2H), 7.01 (td, J = 55.0,30.0 Hz, 3H), 6.48 – 6.41 (m, 1H), 6.37 (d, J = 15.0 Hz, 1H), 6.32 (d, J = 2.5Hz, 1H), 6.27 (s, 1H), 5.44 (d, J = 2.6 Hz, 1H), 3.97 (s, 3H), 3.96 (s, 3H), 1.91 (d, J =5.0 Hz, 3H).

[0075] 13 C NMR (151 MHz, Chloroform- d) δ 196.23, 164.83, 160.83,160.76,146.93,146.67,141.15, 135.81, 135.63, 128.26, 124.35, 111.80,100.86,100.71,109.29, 109.14, 107.72,107.56,78.51, 74.94, 39.92, 39.87, 19.64.

[0076]

[0077] (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diol bis(1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxylate) 1 H NMR (600 MHz, Chloroform- d ) δ 8.01 (d, J = 6.0 Hz, 2H), 6.49 – 6.40(m, 1H), 6.35 (d, J = 12.0 Hz, 1H), 6.32 (s, 1H), 6.26 (s, 1H), 5.47 (d, J =2.3 Hz, 1H), 3.97 (s, 4H), 3.95 (s, 4H), 1.90 (d, J = 12.0 Hz, 3H).

[0078] 13 C NMR (151 MHz, Chloroform- d) δ 196.20, 164.96, 159.90, 159.57,149.55,144.38,142.33,142.38,142.12, 141.81, 141.08, 137.11, 136.98, 128.17,124.31, 121.17, 119.38, 111.83, 111.65, 78.38, 75.05, 40.04, 39.96, 19.59.

[0079] 19 F NMR (565 MHz, Chloroform- d ) δ -61.98, -62.17.

[0080] HR-ESI-MS (m / z 507.1099 [M+H]) + , Cal. 506.3614).

[0081]

[0082] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(5-chloro-1-methyl-1H-pyrazole-4-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(5-chloro-1-methyl-1H-pyrazole-4-carboxylate) 1 H NMR (500 MHz, Chloroform- d ) δ 7.93 (s, 1H), 7.90 (s, 1H), 6.43(dd, J = 15.0, 5.0 Hz, 1H), 6.35 (d, J = 15.0 Hz, 2H), 6.26 (s, 1H), 5.43 (d, J = 2.5 Hz, 1H), 3.85 (s, 3H), 3.84 (s, 3H), 1.88 (d, J = 5.0 Hz, 3H).

[0083] 13 C NMR (151 MHz, Chloroform- d) δ 196.78, 164.96, 160.62, 160.57,141.72, 141.62, 140.69, 132.12, 132.00, 128.36, 124.58, 109.86, 109.76,78.48, 74.71, 36.81, 36.73, 19.64.

[0084]

[0085] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(1,3-dimethyl-1H-pyrazole-4-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(1,3-dimethyl-1H-pyrazole-4-carboxylate) 1 H NMR (500 MHz, Chloroform- d ) δ 7.84 (s, 1H), 7.82 (s, 1H), 6.49 –6.40 (m, 1H), 6.36 (d, J = 10.0 Hz, 2H), 6.26 (s, 1H), 5.38 (d, J = 2.4 Hz,1H), 3.85 (s, 3H), 3.83 (s, 3H), 2.43 (s, 6H), 1.91 (d, J = 5.0 Hz, 3H).

[0086] 13 C NMR (151 MHz, Chloroform- d ) δ 197.54, 165.30, 162.45, 152.14,151.92, 140.43, 135.23, 135.16, 128.18, 124.72, 110.99, 110.80, 78.38,74.22,39.16, 39.07, 19.64, 13.56, 13.46.

[0087] HR-ESI-MS (m / z 399.1666 [M+H]) + , Cal. 398.4190).

[0088]

[0089] (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diol bis(2-oxo-2H-chromene-3-carboxylic acid ester) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(2-oxo-2H-chromene-3-carboxylate) 1 H NMR (400 MHz, Chloroform- d ) δ 8.66 (s, 1H), 8.58 (s, 1H), 7.69 –7.60 (m, 4H), 7.40 – 7.33 (m, 4H), 6.62 (dd, J = 20.0, 4.0 Hz, 1H), 6.51 –6.40 (m, 2H), 6.32 (s, 1H), 5.66 (d, J = 2.8 Hz, 1H), 1.96 (d, J = 4.0 Hz, 3H).

[0090] 13 C NMR (151 MHz, Chloroform- d ) δ 195.70, 164.74, 162.66, 161.76,156.47, 156.25, 155.38, 155.30, 150.06, 149.76, 141.85, 134.95, 129.85 (d, J =3.0 Hz), 128.23, 124.14, 117.72 (d, J = 3.0 Hz), 116.89, 78.94, 76.09, 19.71.

[0091] HR-ESI-MS (m / z 499.1025 [M+H]) + , Cal.498.4430).

[0092]

[0093] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(3,6-dichloropyridinecarboxylate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(3,6-dichloropicolinate) 1 H NMR (500 MHz, Chloroform- d ) δ 7.78 (d, J = 5.0 Hz, 1H), 7.76 (d, J =1.5 Hz, 1H), 7.43 (d, J = 5.0 Hz, 1H), 7.42 (d, J = 5.0 Hz, 1H), 6.66 – 6.56(m, 1H), 6.55 (d, J = 5.0 Hz, 1H), 6.42 (d, J = 20.0 Hz, 1H), 6.31 (s, 1H), 5.72 (d, J = 2.6 Hz, 1H), 1.96 (d, J = 5.0 Hz, 3H).

[0094] 13 C NMR (151 MHz, Chloroform- d ) δ 195.24, 164.51,162.45,162.10,149.31,149.12,146.34,141.70, 141.57, 141.32,131.24, 130.29,128.87, 128.15,128.01, 124.27, 79.20, 76.53,19.71.

[0095]

[0096] (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diol bis(2,6-dichloronicotinate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(2,6-dichloronicotinate) 1 H NMR (500 MHz, Chloroform- d) δ 8.25 (d, J = 8.1 Hz, 1H), 8.19 (d, J =8.1 Hz, 1H), 7.41 (d, J = 8.1 Hz, 1H), 7.38 (d, J = 8.1 Hz, 1H), 6.55 – 6.48(m, 1H), 6.45 (d, J = 2.5 Hz, 1H), 6.41 (d, J = 16.0 Hz, 1H), 6.33 (s, 1H), 5.60 (d, J = 2.6 Hz, 1H), 1.96 (d, J = 6.9 Hz, 4H).

[0097] 13 C NMR (151 MHz, Chloroform- d ) δ 195.01,164.47,163.37,162.99,153.85,153.82,150.52,149.78,143.01,142.67,1 41.60,128.64,124.55,124.23,123.96,123.26,123.03,79.13,76.14,29.78,19.69.

[0098]

[0099] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(4-bromobenzoate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl bis(4-bromobenzoate) 1 H NMR (600 MHz, Chloroform- d ) δ 7.91 (dd, J = 10.9, 8.6 Hz, 4H), 7.59(dd, J = 18.0, 6.0 Hz, 4H), 6.48 – 6.42 (m, 2H), 6.40 (d, J = 18.0 Hz, 1H), 6.32 (s, 1H), 5.53 (d,J = 2.3 Hz, 1H), 1.90 (d, J = 6.0 Hz, 3H).

[0100] 13 C NMR (151 MHz, Chloroform- d ) δ 196.48, 165.18, 165.14, 164.96,140.81, 132.12, 131.92, 131.70, 131.54, 129.16, 128.89, 128.55, 127.98,127.94, 124.60, 79.05, 77.16, 75.56.

[0101]

[0102] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(2,4-dichlorobenzoate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl bis(2,4-dichlorobenzoate) 1 H NMR (600 MHz, Chloroform- d ) δ 7.93 (d, J = 6 Hz, 1H), 7.84 (d, J =12 Hz, 1H), 7.50 (dd, J = 6, 2 Hz, 2H), 7.34 (dd, J = 6, 2 Hz, 1H), 7.32 (dd, J = 6, 2 Hz, 1H), 6.51 (dt, J = 16, 6 Hz, 1H), 6.48 (d, J = 2.6 Hz, 1H), 6.41 (d, J = 18 Hz, 1H), 6.31 (s, 1H), 5.59 (d, J = 2.6 Hz, 1H), 1.94 (d, J = 6 Hz, 3H).

[0103] 13 C NMR (151 MHz, Chloroform- d ) δ 195.90, 164.84, 164.25, 163.92,141.19, 139.24, 135.77, 135.17, 133.21, 132.77, 131.29, 128.60, 127.45,127.22, 126.98, 124.44, 79.03, 75.77, 19.68.

[0104]

[0105] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(3,4,5-trifluorobenzoate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl bis(3,4,5-trifluorobenzoate) 1 H NMR (600 MHz, Chloroform- d ) δ 7.71 (dt, J = 12, 6 Hz, 4H), 6.48 –6.43 (m, 1H), 6.42 (s, 1H), 6.39 (s, 1H), 6.35 (s, 1H), 5.52 (s, 1H), 1.94(d, J = 6 Hz, 3H).

[0106] 13 C NMR (151 MHz, Chloroform- d ) δ 195.50, 164.50, 163.22, 152.08,150.34,141.17, 128.70, 124.80,124.42, 114.96, 114.92, 114.84, 114.80, 114.72,114.69, 79.17, 76.02, 19.72.

[0107] 19 F NMR (565 MHz, Chloroform- d ) δ -131.66, -132.16, -150.60, -151.12.

[0108] HR-ESI-MS (m / z 471.0662 [M+H]) + , Cal. 470.3234).

[0109]

[0110] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(2-(4-fluorophenoxy)acetate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl bis(2-(4-fluorophenoxy)acetate) 1 H NMR (400 MHz, Chloroform- d ) δ 7.00 – 6.92 (m, 4H), 6.89 – 6.83 (m,4H), 6.43 – 6.34 (m, 1H), 6.31 (d, J = 16.6 Hz, 1H), 6.24 (d, J = 5.6 Hz, 1H), 6.21 – 6.17 (m, 1H), 5.38 (d, J = 2.6 Hz, 1H), 4.79 – 4.64 (m, 4H), 1.90 (d, J = 6.2 Hz, 3H).

[0111] 13 C NMR (151 MHz, Chloroform- d ) δ 195.17, 168.58, 164.33, 158.70 (d, J= 3.0 Hz), 157.11 (d, J = 3.0 Hz)153.68 (dd, J = 13.8, 13.6 Hz), 140.99,128.36, 124.12, 116.13 (d, J = 12.3 Hz), 116.00 (d, J = 7.55 Hz), 115.93 (d, J = 3.0 Hz), 115.74 (d, J =7.6 Hz), 78.30, 75.31, 65.55, 29.70, 19.54. 19 F NMR (565 MHz, Chloroform- d ) δ -122.20, -122.55.

[0112] HR-ESI-MS (m / z 459.1251 [M+H]) + , Cal. 458.4138).

[0113]

[0114] (1R,2S)-5-oxo-3-[(E)-1-propen-1-yl]cyclopent-3-ene-1,2-diol bis(2-(4-chlorophenoxy)acetate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diylbis(2-(4-chlorophenoxy)acetate) 1 H NMR (400 MHz, Chloroform- d ) δ 7.22 (dd, J = 9.0, 2.4 Hz, 4H), 6.83(dd, J = 9.0, 4.5 Hz, 4H), 6.43 – 6.30 (m, 1H), 6.25 (d, J = 19.0 Hz, 2H), 6.18(d, J = 2.4 Hz, 1H), 5.39 (d, J = 2.6 Hz, 1H), 4.81 – 4.65 (m, 4H), 1.90 (d, J =6.2 Hz, 3H).

[0115] 13 C NMR (151 MHz, Chloroform- d )δ195.21,168.53,168.48,168.40,164.40,156.24, 156.15, 141.22, 129.74,129.69, 129.62, 128.50, 127.12,126.97,124.22,116.20,116.09, 115.90, 78.43,75.46, 65.28, 65.12, 29.84,19.71.

[0116] HR-ESI-MS (m / z 492.0697 [M+H]) + , Cal.

[0117] (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diol(2E,2'E)-bis(3-(2,4-dichlorophenyl)acrylate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl(2E,2'E)-bis(3-(2,4-dichlorophenyl)acrylate) 1 H NMR (600 MHz, Chloroform- d ) δ 8.10 (dd, J = 12.0, 6.0 Hz, 2H), 7.58(dd, J = 13.5, 8.3 Hz, 2H), 7.46 (d, J = 2.1 Hz, 1H), 7.44 (d, J = 2.1 Hz, 1H), 7.29 (d, J = 6.0 Hz, 1H), 7.28 (d, J = 1.8 Hz, 1H)6.49 (d, J = 1.5 Hz, 1H), 6.48– 6.42 (m, 2H), 6.39 (d, J = 18.0 Hz, 1H), 6.32 (d, J = 2.2 Hz, 1H), 6.29 (s,1H), 5.41 (d, J = 2.5 Hz, 1H), 1.94 (d, J = 6.0 Hz, 3H).

[0118] 13 C NMR (151 MHz, Chloroform- d) δ 196.75,165.38, 165.04,141.25,141.08, 140.68, 136.94,136.71,135.79,135.76,130.95,130.76,130.13, 130.06,128.47, 128.32, 127.67, 127.62, 124.50, 119.49, 78.68,75.01, 19.63.

[0119] HR-ESI-MS (m / z 552.9953 [M+H]) + , Cal. 552.2250).

[0120]

[0121] (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-en-1,2-diol bis(2-bromoacetate) (1R,2S)-5-oxo-3-((E)-prop-1-en-1-yl)cyclopent-3-ene-1,2-diyl bis(2-bromoacetate) 1 H NMR (500 MHz, Chloroform- d ) δ 6.46 – 6.38 (m, 1H), 6.34 (d, J =20.0 Hz, 1H), 6.22 (s, 1H), 6.10 (d, J = 2.6 Hz, 1H), 5.30 (d, J = 5.0 Hz, 1H), 3.94 (s, 2H), 3.88 (d, J =5.0 Hz, 2H), 1.95 (d, J = 10.0 Hz, 3H).

[0122] 13 C NMR (151 MHz, Chloroform- d ) δ 195.20, 166.63, 164.46, 141.59, 128.44, 124.02, 78.94, 75.92, 29.69, 24.96, 24.81, 19.57.

[0123] Example 3 Herbicidal Activity Test of Compounds The experiment employed the petri dish culture method. A slight modification to the experimental protocol was made: first, all weed seeds to be tested were disinfected with 75% alcohol and then rinsed multiple times with purified water. After rinsing, the seeds were soaked in purified water for 6 hours. Then, the weed seeds were placed in petri dishes with two layers of filter paper at the bottom, and the dishes were placed in an artificial climate incubator with closed light for 48 hours to promote germination at 28℃ and 70%-80% relative humidity. After the seeds showed signs of sprouting, weed seeds with similar growth stages were selected as experimental subjects for a pre-emergence weed control activity test. Two sheets of filter paper were laid flat in each well of a 12-well plate, and 6-8 sprouted seeds were placed in each well, labeled and numbered. Subsequently, 0.4 mL of the agent (enough to moisten the filter paper and just submerge the seeds) was added to each well to treat the weed seeds. Each treatment was repeated three times. After treatment, the 12-well plate was placed in an artificial climate incubator and cultured for 4-5 days under the conditions of 25-27 ℃, 5000 lx light, a day:night cycle of 16 h:8 h, and a relative humidity of 70%-80%. After 4-5 days of observation, the plumules and radicles of 5 seeds with basically the same phenotype were measured in each well. The growth inhibition rate of each treatment agent on the plumules and radicles of weed seeds was calculated according to the following formula. At the same time, a 1 mM solution of the active compound was used as the test stock solution. Five groups of test solutions of appropriate concentrations were prepared by dilution, and the growth inhibition rate of the compound on the radicles and plumules of weeds under different concentration gradients was determined. Data analysis was performed using Graphpad Prism 9.5 software, and the logarithm of the relationship between inhibition rate and concentration was fitted. 10 [Test concentration( m The half-maximum effective concentration (EC50) of the target compound on the radicle and plumule of weeds was obtained. 50 ), 95% confidence interval and R 2 Isoparameter data were collected, and EC50 values ​​of each compound on the radicle and plumule of weeds were plotted. 50 picture.

[0124] Inhibition rate (%) = ( L 对照组 - L 处理组 ) / L 对照组 ×100% in, L This indicates the length of the embryo or radicle of each weed. Drug preparation: Accurately weigh 3 mg of the target product into a 20 mL glass bottle, add an appropriate amount of... N , NThe solution was dissolved in dimethylformamide (DMF) or methanol by ultrasonication, and then diluted with 0.1% Tween-80 and the corresponding volume of distilled water to the required concentration to prepare a 0.3 mg / mL formulation. The commercial herbicide glyphosate was used as a control; a mixture of equal volumes of DMF or methanol with Tween-80 served as a blank control group.

[0125] Table 2. Evaluation of seed germination experiments of Aspergillus terrestris ester derivatives

[0126] "-": Not tested; different letters in the same column represent significant differences (p<0.05).

[0127] The anti-weed spectrum of some compounds was studied. At a concentration of 1 mM, compounds II-16, II-17, and II-18 completely inhibited the growth of the radicles of the four weeds, but their inhibitory effect on the plumules was slightly weaker. Compounds II-21 and II-22 showed excellent predatory inhibition effects against *Amaranthus retroflexus*, *Hemiberlesia asiatica*, *Lysimachia christinae*, and *Lysimachia ryegrass* at a concentration of 1 mM. Figure 2-6 It has higher activity than the commercial herbicide glyphosate.

[0128] Table 3. EC50 of some target compounds measured in the radicle of *Amaranthus retroflexus*. 50 value

[0129] Table 4. EC50 of some target compounds measured in the embryo of *Amaranthus retroflexus* 50 value

[0130] Tables 3 and 4 were obtained through half-maximal effect concentration calculation and data fitting analysis. Figure 7 and 8 As drug concentration increased, the lengths of the plumules and radicles of *Amaranthus retroflexus* decreased significantly, exhibiting a strong concentration-dependent effect. The EC50 of the target compound on the radicles and plumules of *Amaranthus retroflexus* was... 50 The values ​​were all lower than those of terbufoten. Compared with terbufoten, the three target compounds showed a 1.1–2.8-fold increase in activity against the radicle of *Amaranthus retroflexus* and a 1.1–2.6-fold increase in activity against the plumule. The optimal compound II-21 showed the best activity against the radicle (EC50). 50 =54.1 m M) compared to terazosin (EC) 50 = 152 m M) is about 2.8 times higher than commercial glyphosate (EC) 50 = 83.7 mM) was nearly 1.6 times higher; compound II-21 showed activity against embryonic germ (EC) 50 = 98.1 m M) compared to terazosin (EC) 50 = 253 m M) is nearly 2.6 times higher, and also higher than commercially available glyphosate (EC) 50 = 313 m The M) was nearly 3.2 times higher. This shows that introducing the chloroethyl ester structural fragment into the dihydroxyl site of terbinafine can significantly improve the inhibitory effect of terbinafine on amaranth.

[0131] Table 5. Measurement of EC5 in the radicle of *Cat's Eye* for some target compounds 50 value

[0132] Table 6. Measurement of EC5 of some target compounds in cat's eye grass germ 50 value

[0133] The results of half-maximal effect concentration calculation and data fitting analysis are shown in Tables 5-6 and 6. Figure 9-12 As shown. The EC50 of compounds II-21 and II-22 on the radicle of *Corydalis yanhusuo*. 50 132 and 104 respectively m M, compared to terazosin (EC) 50 = 623 m M) activity was increased by 4.7 to 6.0 times, which is lower than that of commercially available glyphosate (EC). 50 = 32.8 m M) activity; EC activity in embryo 50 They are 65 and 231 respectively. m M, compared to terazosin (EC) 50 = 794 m The activity of glyphosate (M) was increased by 3.4 to 12 times, with II-21 showing even better activity against the embryo than commercially available glyphosate (EC). 50 = 121 m The activity of M) is 1.9 times that of glyphosate.

[0134] For compounds II-16~II-18, although their EC values ​​for radicles were not obtained... 50 Values, but from the complete inhibition concentration analysis of the radicle, terazosin was at 2000 m Only M can completely inhibit radicle growth, while compounds II-16~II-18 at 25 m At M, the radicle is still completely suppressed ( Figure 9 and 10It can be inferred that compounds II-16~II-18 have at least 80 times higher activity against radicles than terbinazone; and their EC activity against radicles... 50 Then it is between 20 and 90. m Between M and terazosin (EC) 50 = 794 m M) exhibits better activity, with an activity increase of 8.8 to 40 times, superior to commercially available glyphosate (EC). 50 = 121 m M) activity, of which II-18 has 6 times the activity of glyphosate against cat's eye grass germ. Even when the concentration is reduced to 25 m Compounds M, II-16, II-17, and II-18 can completely inhibit the growth of the embryonic root of *Corydalis yanhusuo*; furthermore, II-18 at 100... m At M concentration, the inhibition rate on the embryo is also close to 100%. This can be seen from... Figure 7 It can be seen that as the drug concentration decreases, this phenomenon of dwarfing and swelling of the embryo gradually subsides. From the chemical structure analysis, the introduction of phenoxyethyl fragments with different halogen substitutions onto the dihydroxyl groups of terbinafine can greatly enhance its inhibitory effect on the embryonic roots and embryos of Aspergillus flavus, and the inhibitory effect is II-16 < II-17 < II-18 (i.e., phenoxyethyl para-halogen substitution -F < -Cl < -Br).

[0135] In summary, the three target compounds II-9, II-21, and II-22 exhibited EC50 activity against the radicle and plumule of *Amaranthus retroflexus*. 50 The values ​​were all lower than those of terbufoten. Compared with terbufoten, the three target compounds showed a 1.1–2.8-fold increase in activity against the radicle of *Amaranthus retroflexus* and a 1.1–2.6-fold increase in activity against the plumule. The optimal compound II-21 showed the best activity against the radicle (EC50). 50 = 54.1 m M) compared to terazosin (EC) 50 = 152 m M) is about 2.8 times higher than commercial glyphosate (EC) 50 = 83.7 m M) was nearly 1.6 times higher; compound II-21 showed activity against embryonic germ (EC) 50 = 98.1 m M) compared to terazosin (EC) 50 = 253 m M) is nearly 2.6 times higher, and also higher than commercially available glyphosate (EC) 50 = 313 m The M) was nearly 3.2 times higher. This shows that introducing the chloroethyl ester structural fragment into the dihydroxyl site of terbinafine can significantly improve the inhibitory effect of terbinafine on amaranth.

[0136] The three target compounds, II-9, II-21, and II-22, showed EC50 activity in the radicle and plumule of *Corydalis yanhusuo*. 50 The values ​​were all lower than those of terbinafine, and the EC50 values ​​of the target compound on the radicle were lower. 50 In 104~463 m Around M, compared to terazosin (EC) 50 = 623 m M) showed better activity, with an activity increase of 1.4 to 6.0 times; EC on embryos 50 Between 65 and 395 m Around M, compared to terazosin (EC) 50 = 794 m M) exhibits better activity, with an activity increase of 2.0 to 12.2 times, approaching or even surpassing that of commercially available glyphosate (EC). 50 = 121 m M) activity; for compounds II-16~II-18, based on the complete inhibition concentration analysis of the radicle, it can be inferred that the activity of compounds II-16~II-18 on the radicle is at least 80 times higher than that of terbinafine; EC on the radicle 50 Then it is between 20 and 90. m Between M and terazosin (EC) 50 = 794 m M) exhibits better activity, with an activity increase of 8.8 to 40 times, superior to commercially available glyphosate (EC). 50 = 121 m M) activity, of which II-18 has 6 times the activity of glyphosate on cat's eye grass embryos.

[0137] The above description is merely an embodiment of the present invention, and the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims of the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principle of the present invention should be included within the scope of protection of the present invention.

Claims

1. A terbinazone derivative, characterized in that, The structural formula of the terbinazone derivatives is shown in Formula 1: In the aforementioned structural formula 1, the structure of R1 includes hydrogen and C. 1-3 Alkyl, C 2-3 alkenyl, C 2-3 alkynyl group, C 1-3 Alkoxy, C 3-5 cycloalkyl, C 3-5 Cycloalkyloxy, halogen, nitro, cyano, trifluoromethyl, 3-7 membered heterocyclic groups, C 6-10 Aryl, C 6-10 At least one of the aromatic compounds.

2. The terbinazone derivative according to claim 1, characterized in that, The C 6-10 Aryl, C 6-10 The aromatic heterol group is an unsubstituted or R2-substituted C 6-10 Aryl, C 6-10 Aromatic heteroalkyl groups, of which: R2 is a halogen, C 1-3 At least one of alkoxy, difluoromethyl, and trifluoromethyl.

3. The terbinazone derivative according to claim 1, characterized in that, R1 includes: , , , , , , , , , , , , , , , , , , At least one of ClCH2- and BrCH2-.

4. A method for preparing terbinazone derivatives according to any one of claims 1-3, characterized in that, The method includes the following steps: Using anhydrous dichloromethane as the reaction solvent, at least one of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl), dicyclohexylcarbodiimide (DCC), and diisopropylcarbodiimide (DIC) as the condensing agent, and 4-dimethylaminopyridine as the catalyst, terbinafine is reacted with different substrate carboxylic acids to obtain the terbinafine ester derivatives.

5. The method according to claim 4, characterized in that, The method further includes the step of separating and purifying the obtained terbinazone derivatives.

6. The method according to claim 4, characterized in that, The method also includes the step of preparing terbinafine.

7. The method according to claim 6, characterized in that, The specific steps for preparing terbinafine include the following operations: Aspergillus terreus was obtained by fermenting Aspergillus with accession number CGMCC No. 20251, filtering the fermentation broth, and then extracting the active ingredient.

8. A composition, characterized in that, The composition comprises at least the terbinazone derivatives as described in any one of claims 1-3 and agriculturally acceptable additives.

9. The use of the terbinafine ester derivatives according to any one of claims 1-3, the method according to any one of claims 4-7, or the composition according to claim 8 in the preparation of herbicidal products.

10. The application according to claim 9, characterized in that, The herbicide product includes at least one of the genera Amaranth, Euphorbia, Euphorbia, and Lorula.

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