Piperidone monoterpenoids, preparation method and application thereof, and herbicide composition

Abstract

The invention provides a piperonone type monoterpenoid compound, a preparation method and application thereof and a herbicide composition, and belongs to the technical field of agricultural herbicides. The piperonone type monoterpenoids provided by the invention have structures as shown in formulas I-IV. According to the present invention, Mureupiperione A (a compound represented by a formula I), Mureupiperione B (a compound represented by a formula II), (+)-(4S, 6R)-6-hydroxypyriperione (a compound represented by a formula III) and (-)-(4R, 6S)-6-hydroxypyriperione (a compound represented by a formula IV) are separated from a rutaceae murraya paniculata plant, and the provided piperonone type monoterpene compound provides excellent herbicidal activity for a variety of weeds in farmlands and non-cultivated lands, can be used for preparing herbicidal preparations, and can be used for preparing herbicidal preparations. The compound can be used for preparing herbicides in the agricultural field or other fields.

Description

Technical Field

[0001] The invention belongs to the technical field of agricultural herbicides, and particularly relates to a piperitone-type monoterpenoid compound, a preparation method and application thereof, and a herbicide composition. Background Art

[0002] Farmland weeds, as a major biotic stress, pose a serious threat to agricultural production. In addition to competing with crops for biological resources such as light, water, space, and nutrients, some weeds serve as important intermediate hosts for several pests and diseases. To improve crop yield and quality, there is increasing reliance on synthetic herbicides to control weeds and the pests that parasitize them. According to recent data, herbicides are the most commonly used pesticides worldwide, accounting for over 60% of agricultural pesticide use. While highly effective in controlling weeds, their long-term and cumulative use has led to the acquisition of resistance in some weeds, resulting in environmental pollution and potential impacts on other organisms. To address this, new strategies are being proposed globally to reduce the use of synthetic herbicides, such as novel green herbicides, synthetic herbicides encapsulated in nanoparticles, and organic mulches, to prevent the spread of weeds and achieve sustainable weed management.

[0003] Natural products have special chemical structures and extensive biological activities. They are necessary raw materials for the development of new green herbicides and are also one of the important sources of pesticide lead compounds. Summary of the Invention

[0004] The present invention aims to provide a piperitone-type monoterpenoid compound, a preparation method and application thereof, and a herbicide composition. The piperitone-type monoterpenoid compound provided by the present invention exhibits excellent herbicidal activity against various weeds in farmland and non-cultivated land, and is extracted from natural products, thus being a new type of green herbicide.

[0005] In order to achieve the purpose of the present invention, the present invention provides the following technical solutions:

[0006] A piperitone-type monoterpenoid compound having a structure shown in Formula I or Formula II:

[0007]

[0008] The present invention also provides a method for preparing the piperitone-type monoterpenoid compound described in the above technical solution, comprising the following steps:

[0009] extracting the plant raw material with methanol-water solution and concentrating the extract to obtain an alcohol extract; the plant raw material comprises one or more plants of the genus Murraya, the genus Litsea and the genus Pyrola;

[0010] The alcohol extract is subjected to a first silica gel column chromatography separation, with petroleum ether, ethyl acetate and methanol as the mobile phases, to obtain petroleum ether, ethyl acetate and methanol elution fractions, respectively;

[0011] The ethyl acetate elution fraction was subjected to RP-18 reverse phase column chromatography to obtain five fractions A to E after gradient elution; the mobile phase for the gradient elution was methanol / water with a volume ratio of 40:60, 60:40, 80:20, 90:10, and 100:0;

[0012] Fraction D was subjected to a second silica gel column chromatography separation, and after gradient elution, the same fractions were combined to obtain four fractions D1 to D4; the mobile phase for the gradient elution was petroleum ether / acetone in volume ratios of 10:0, 10:1, 5:1, 3:1, 1:1, and 0:10;

[0013] The D2 portion was separated by a third silica gel column chromatography, and after elution, the same components were combined into 4 portions D 2-1 ~D 2-4 The mobile phase for elution was petroleum ether / acetone in a volume ratio of 5:1;

[0014] D 2-3 The fourth silica gel column chromatography was performed to separate the D 2-3-1 and D 2-3-2 part; the elution mobile phase was petroleum ether / acetone with a volume ratio of 5:1;

[0015] D 2-3-1 and D 2-3-2 The parts were separated and purified by high performance liquid chromatography to obtain the compound of formula I and the compound of formula II respectively; the mobile phase of the high performance liquid chromatography was methanol / water with a volume ratio of 9:1.

[0016] Preferably, the plant of the genus Murraya includes Murraya oleifera.

[0017] Preferably, the extraction is performed 3 to 5 times; the temperature of each extraction is 60 to 80° C., and the time is 1 to 3 hours; the mass ratio of the plant material to methanol is 1:3 to 5; and the mass concentration of the methanol aqueous solution is 90 to 95%.

[0018] Preferably, the particle size of the silica gel in the first, second, third and fourth silica gel column chromatography separations is 200-300 mesh.

[0019] Preferably, it also includes: D 2-2 The residues were separated and purified by high performance liquid chromatography to obtain compounds of formula III and formula IV; the mobile phase of the high performance liquid chromatography was methanol / water in a volume ratio of 9:1;

[0020]

[0021] The present invention also provides a use of a piperitone-type monoterpenoid compound or a salt thereof in a herbicide. The piperitone-type monoterpenoid compound has a structure represented by any of the following structural formulas:

[0022]

[0023] Preferably, the piperitone-type monoterpenoid compound or its salt is suitable for one or more of grass weeds, sedge weeds and broadleaf weeds.

[0024] Preferably, the weeds include one or more of barnyard grass, crabgrass and Amaranthus retroflexus.

[0025] The present invention provides a herbicide composition, comprising an active component and an adjuvant; the active component is a piperitone-type monoterpenoid compound or a salt thereof;

[0026] The adjuvant includes one or more of insecticides, fungicides and plant growth regulators;

[0027] The piperitone-type monoterpenoid compound has a structure shown in any of the following structural formulas:

[0028]

[0029] The present invention provides a piperitone-type monoterpenoid compound having the structures shown in Formula I and Formula II. The present invention provides Mureupiperitone A (Formula I compound), Mureupiperitone B (Formula II compound), (+)-(4S,6R)-6-hydroxy-piperitone (Formula III compound), and (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV compound), isolated from Mureus odoratus of the genus Mureus in the family Rutaceae. The piperitone-type monoterpenoid compound provided by the present invention exhibits excellent herbicidal activity against various weeds in farmland and non-arable land, and can be used to prepare herbicides in the agricultural field or other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0031] Figure 1 For the compound of formula I 1 H NMR spectrum;

[0032] Figure 2 For the compound of formula I 13C-NMR spectrum;

[0033] Figure 3 For the compound of formula II 1 H NMR spectrum;

[0034] Figure 4 For the compound of formula II 13 C-NMR spectrum;

[0035] Figure 5 For the compound of formula III 13 C-NMR spectrum;

[0036] Figure 6 For the compound of formula IV 13 C-NMR spectrum. DETAILED DESCRIPTION

[0037] The present invention provides a piperitone-type monoterpenoid compound having the following structure:

[0038]

[0039] The present invention also provides a method for preparing the piperitone-type monoterpenoid compound described in the above technical solution, comprising the following steps:

[0040] The present invention also provides a method for preparing the piperitone-type monoterpenoid compound according to the above technical solution, comprising the following steps:

[0041] extracting the plant raw material with methanol-water solution and concentrating the extract to obtain an alcohol extract; the plant raw material comprises one or more plants of the genus Murraya, the genus Litsea and the genus Pyrola;

[0042] The alcohol extract is subjected to a first silica gel column chromatography separation, with petroleum ether, ethyl acetate and methanol as the mobile phases, to obtain petroleum ether, ethyl acetate and methanol elution fractions, respectively;

[0043] The ethyl acetate elution fraction was subjected to RP-18 reverse phase column chromatography to obtain five fractions A to E after gradient elution; the mobile phase for the gradient elution was methanol / water with a volume ratio of 40:60, 60:40, 80:20, 90:10, and 100:0;

[0044] Fraction D was subjected to a second silica gel column chromatography separation, and after gradient elution, the same fractions were combined to obtain four fractions D1 to D4; the mobile phase for the gradient elution was petroleum ether / acetone in volume ratios of 10:0, 10:1, 5:1, 3:1, 1:1, and 0:10;

[0045] The D2 portion was separated by a third silica gel column chromatography, and after elution, the same components were combined into 4 portions D 2-1 ~D 2-4The mobile phase for elution was petroleum ether / acetone in a volume ratio of 5:1;

[0046] D 2-3 The fourth silica gel column chromatography was performed to separate the D 2-3-1 and D 2-3-2 part; the elution mobile phase was petroleum ether / acetone with a volume ratio of 5:1;

[0047] D 2-3-1 and D 2-3-2 The parts were separated and purified by high performance liquid chromatography to obtain the compound of formula I and the compound of formula II respectively; the mobile phase of the high performance liquid chromatography was methanol / water with a volume ratio of 9:1.

[0048] In the present invention, the plant raw material includes one of the genus Murraya, the genus Litsea and the genus Pyrola; the genus Murraya can specifically be Murraya oleifera; the plant raw material can be the branches, leaves or stems of the plant.

[0049] In the present invention, the extraction is performed 3 to 5 times; the temperature of each extraction is 60 to 80° C., and the time is 1 to 3 hours; the mass ratio of the plant material to methanol is 1:3 to 5; and the mass concentration of the methanol is 90 to 95%.

[0050] In the present invention, the D2 portion is subjected to a third silica gel column chromatography separation, and after elution, the same components are combined into four portions D 2-1 ~D 2-4 ; Among them, according to the component elution time and the same component is combined into 4 parts D 2-1 ~D 2-4 .

[0051] In the present invention, D 2-2 The residues were separated and purified by high performance liquid chromatography to obtain compounds of formula III and formula IV; the mobile phase of the high performance liquid chromatography was methanol / water in a volume ratio of 9:1;

[0052]

[0053] The present invention also provides a use of a piperitone-type monoterpenoid compound or a salt thereof in the preparation of a herbicide. The piperitone-type monoterpenoid compound has the following structure:

[0054]

[0055]

[0056] In the present invention, the piperitone-type monoterpenoid compound or its salt is suitable for crop field weeds or horticultural weeds; the crop field weeds include rice field weeds, wheat field weeds and corn field weeds;

[0057] The rice field weeds include grass weeds, specifically one or more of Echinochloa crusgalli, Leptochloa chinensis, Digitaria sanguinalis, Lishi grass and Goosegrass; sedge weeds, specifically one or more of Cyperus dimorphus, Cyperus angustifolia and Schizonepeta tenuifolia; broadleaf weeds, specifically one or more of Amaranthus water spinach, Commelina tongue, Polygonum sylvestris, Moshangcai and Echinops sphenanthera.

[0058] The wheat field weeds include grass weeds, specifically Alopecurus ovata, Poa annua, Hard grass, Gnaphalium spp., Wild oats, Goosegrass and Setaria viridis; broadleaf weeds, specifically one or more of Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp., Gnaphalium spp. and Bifida odorata.

[0059] The cornfield weeds include grassy cornfield weeds, specifically one or more of crabgrass, barnyard grass, foxtail grass, barnyard grass and goosegrass; broadleaf cornfield weeds, specifically one or more of knotweed, wild amaranth, purslane, amaranth, cyperus, field bindweed, duckweed, prickly lettuce and sonchus.

[0060] In the present invention, the piperitone-type monoterpenoid compounds have a better control effect on barnyard grass, crabgrass and Amaranthus retroflexus.

[0061] The present invention also provides a herbicide composition, comprising an active component and an adjuvant; the active component is a piperitone-type monoterpenoid compound or a salt thereof;

[0062] The adjuvant includes one or more of insecticides, fungicides and plant growth regulators.

[0063] In the present invention, the piperitone-type monoterpenoid compound can be used alone as a herbicide or combined with other adjuvants for the prevention and control of various farmland weeds.

[0064] In the present invention, the adjuvant includes phenoxycarboxylic acid, specifically 2,4-D and / or 2-methyl-4-chloro-4-pyrazoline; aromatic oxyphenoxy propionate, specifically one or more of quizalofop-p-ethyl, fluazifop-p-ethyl, fluazifop-p-ethyl, cyhalofop-butyl, quizalofop-butyl, clodinafop-butyl and oxadiazol-butyl; dinitroaniline, specifically trifluralin and / or pendimethalin; triazine, specifically atrazine, promethazine, cyanamide, cyhalofop-butyl, cyhalofop-butyl, cyhalofop-butyl, clodinafop-butyl and oxadiazol-butyl; sulfonylureas, specifically mesosulfuron, bensulfuron-methyl, benzylsulfuron-methyl, nicosulfuron-methyl, chlorsulfuron-methyl, metsulfuron-methyl, chlorimuron-methyl, pyrazosulfuron-methyl, thifensulfuron-methyl, ethametsulfuron-methyl, ethoxysulfuron-methyl, fluorosulfuron-methyl, fluorosulfuron-methyl, sulfonyl ... The invention relates to the following: oxazolidinone, chlorpyrifos-sodium, trifloxysulfuron-sodium; sulfonamides, specifically imidazolesulfonamide, bisfluorosulfonamide, pentafluorosulfonamide, pyrasulfuron; organophosphorus, specifically glyphosate, glufosinate, bialaphos, cypermethrin); triketones, specifically mesotrione, benzylpezil; bipyridyls, specifically paraquat, diquat; imidazolinones, specifically imidazoleacetic acid, methoxyfen-2-methylpyrrolidone); pyrimidine salicylic acids, specifically pyrimidine oxime-butyl, bispyribac-sodium; carbamates, specifically cyprodinil, cyprodinil, betamethrin; cyclohexenones, specifically sethoxydim, sethoxydim; substituted ureas, specifically diuron, isoproturon; cyclic imines, specifically oxadiazon, fluazifop and others, specifically quinclorac, isoclomethasone, cloflupyr, chlorpyrifos, bromoxynil, pinoxaden.

[0065] In the present invention, in order to achieve better control effects, the dosage and ratio of the piperitone-type monoterpenes can be changed according to various factors, such as the nature of the compound, the crop to be protected, the type of weeds, the growth period of the crop and weeds, climatic conditions, application technology, the dosage form used, etc.

[0066] In the present invention, the piperitone-type monoterpenoid compound can also be prepared into a medicinal fertilizer for use.

[0067] The present invention has no particular limitation on the formulation of the herbicide composition. In a specific embodiment, a piperitone-type monoterpenoid compound or a salt thereof can be dissolved or dispersed in a medium as an active ingredient, and adsorbed on a carrier or formulated into a formulation for use. Specifically, the formulation can be in the form of a concentrated emulsion, a powder, an emulsifiable concentrate, an aqueous emulsion, a paste, a disintegrant, a fumigant, a bait, a gel, a granule, a microcapsule, a seed coating agent, a suspension, a tablet, a water-soluble liquid, a water-dispersible agent, a dry suspension, a wettable powder, and an ultra-low volume solution.

[0068] The herbicide composition of the present invention further comprises a liquid carrier or a solid carrier, and a surfactant; the present invention has no particular limitation on the liquid carrier, solid carrier and surfactant, and commercially available products well known to those skilled in the art may be used.

[0069] In the present invention, the herbicide composition is applied to weeds or the medium in which they grow to kill weeds. The application amount of the herbicide composition is appropriately adjusted according to the weed content. In a specific embodiment, a dosage of 10 to 5000 g of a piperitone-type monoterpenoid compound per hectare can achieve an ideal control effect. The dosage can further be 10 to 1000 g or 20 to 500 g.

[0070] To further illustrate the present invention, the piperitone-type monoterpenoid compounds, their preparation methods and applications, and their herbicide compositions provided by the present invention are described in detail below with reference to the accompanying drawings and examples. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0071] Example 1

[0072] Weigh 3.6 kg of Murraya odorifera branches and leaves, air-dry and crush, then add 3 times the weight of 95% methanol and extract under reflux for 3 times at 60°C for 3 hours each time. Filter and combine the three extracts, and concentrate under reduced pressure to an extract to obtain a methanol extract (191.4 g). The obtained methanol extract is mixed with 100-200 mesh silica gel and separated by column chromatography using 200-300 mesh silica gel. The mobile phase is eluted with 5 column volumes of petroleum ether, ethyl acetate, and methanol, respectively, to obtain a petroleum ether fraction, an ethyl acetate fraction, and a methanol fraction.

[0073] The ethyl acetate fraction (51.4 g) was chromatographed on an RP-18 reverse phase column using methanol / water as the mobile phase for gradient elution (v / v, 40:60, 60:40, 80:20, 90:10, 100:0) to obtain five fractions AE;

[0074] D (7.3 g) was separated by chromatography on a 200-300 mesh silica gel column using a gradient elution method of petroleum ether / acetone (v / v, 10:0, 10:1, 5:1, 3:1, 1:1, 0:10) to obtain four fractions D1-D4;

[0075] D2 (0.7 g) was separated by chromatography on a 200-300 mesh silica gel column using petroleum ether-acetone (v / v, 5:1) as the eluent to obtain four fractions D 2-1 ~D 2-4 ;

[0076] D 2-2The product was separated and purified by HPLC using methanol / water (CH3OH / H2O, v / v, 90:10) as eluent to obtain the compound of formula III (54 mg) and the compound of formula IV (67 mg);

[0077] D 2-3 The product was separated by 200-300 mesh silica gel column chromatography using petroleum ether-acetone (v / v, 5:1) as eluent to obtain two fractions D 2-3-1 and D 2-3-2 . D 2-3-1 and D 2-3-2 The products were separated and purified by HPLC using methanol / water (CH3OH / H2O, v / v, 90:10) as eluent to give the compound of formula I (56 mg) and the compound of formula II (14 mg).

[0078] Formulas I to IV were identified using nuclear magnetic resonance, mass spectrometry, and optical rotation. The specific physicochemical properties and spectral data are as follows:

[0079] Compound of formula I, light yellow oil, [α] 20 D =-67.5(c 0.11,MeOH).UV(MeOH)λ max (logε)236(3.7)nm.IR(KBr)v max ,2972,2866,1733,1671,883cm -1 ;HR-ESI-MS m / z 233.1153[M+Na] + . 1 H(400MHz) 1 H-NMR (400 MHz, CDCl3, δ, ppm, J / Hz) and 13 C-NMR (100 MHz, CDCl3, δ, ppm). The specific data are shown in Tables 1 and 2.

[0080] Compound of formula II, pale yellow oil, [α] 20 D =-24.2(c 0.10,MeOH).IR(KBr)v max ,3406,2969,2872,1721,1073.HR-ESI-MSm / z 193.1204[M+Na] + . 1 H-NMR (400 MHz, CDCl3, δ, ppm, J / Hz) and 13 C-NMR (100 MHz, CDCl3, δ, ppm). The specific data are shown in Tables 1 and 2.

[0081] Compound of formula III, pale yellow oil, 1 H-NMR (400 MHz, CDCl3, δ, ppm, J / Hz) and 13 C-NMR (100 MHz, CDCl3, δ, ppm). The specific data are shown in Tables 1 and 2.

[0082] Compound of formula IV, light yellow oil, 1 H-NMR (400 MHz, CDCl3, δ, ppm, J / Hz) and 13 C-NMR (100 MHz, CDCl3, δ, ppm). The specific data are shown in Tables 1 and 2.

[0083] Table 1 Proton spectrum data of compounds of formula I to formula IV (400 MHz, J / Hz).

[0084]

[0085]

[0086] Table 2 Carbon spectrum data of compounds of formula I to formula IV (101 MHz, ppm)

[0087]

[0088] From the above results, it can be seen that the compounds of formula I and formula II are new compounds. The structure of the compound of formula I is: (-)-(4S,6R)-4-Hydroxy-6-isopropyl-3-methylcyclohex-2-enone, and it is named: Murreuchrestin A; the structure of the compound of formula II is: (-)-(1R,4R,6R)-6-hydroxy-4-isopropyl-1-methylcyclohexanone, and it is named: mureupiperitone B; the compounds of formula III and formula IV are known compounds. The compound of formula III is: (+)-(4S,6R)-6-hydroxy-piperitone, and the compound of formula IV is: (-)-(4R,6S)-6-hydroxy-piperitone.

[0089] Test Example 1

[0090] Mureupiperitone A (Formula I), Mureupiperitone B (Formula II), (+)-(4S,6R)-6-hydroxy-piperitone (Formula III), and (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV) were tested for their indoor herbicidal activity.

[0091] 1. Seed germination test

[0092] The herbicidal activity of mureupiperitone A, mureupiperitone B, (+)-(4S,6R)-6-hydroxy-piperitone or (-)-(4R,6S)-6-hydroxy-piperitone against three weeds was determined using a Petri dish assay. The concentration of each test compound was 300 μg / mL. The inhibition rates of weed seed germination rates and seedling growth are shown in Tables 3 and 4.

[0093] The specific test method is as follows: Mureupiperitone A, Mureupiperitone B, (+)-(4S,6R)-6-hydroxy-piperitone and (-)-(4R,6S)-6-hydroxy-piperitone are fully dissolved in dimethyl sulfoxide (DMSO) to form mother liquors, and then a 0.1% Tween 80 (polysorbate 80) aqueous solution is added to the mother liquors so that the concentrations of Mureupiperitone A, Mureupiperitone B, (+)-(4S,6R)-6-hydroxy-piperitone and (-)-(4R,6S)-6-hydroxy-piperitone are all 300 μg / mL. Two filter papers were spread in each Petri dish (60 mm in diameter). The filter papers were moistened with 3 mL of Mureupiperitone A, Mureupiperitone B, (+)-(4S,6R)-6-hydroxy-piperitone, and (-)-(4R,6S)-6-hydroxy-piperitone solution, respectively. A 0.1% Tween 80 and 0.9% DMSO aqueous solution were used as controls. Weed seeds were released from dormancy with 0.8% gibberellin, sterilized with 2% sodium hypochlorite solution for 15 min, and then rinsed three times with deionized water. Twenty weed seeds were randomly selected and evenly distributed in each Petri dish. Each treatment was repeated three times. The treated seeds were incubated in an incubator at 25 ± 1°C, 78% relative humidity, and a photoperiod of 12 h:12 h (light:dark). The number of germinated seeds was counted after 3 days. The seed germination inhibition rate was calculated according to formulas (1) and (2):

[0094]

[0095] 2. Seedling growth test

[0096] Mature and plump seeds were soaked in deionized water at room temperature for 24 hours. After rinsing with deionized water, the germinated seeds were placed in a Petri dish with two layers of filter paper and the filter paper was moistened with 3 mL of a 300 μg / mL solution of Mureupiperitone A, Mureupiperitone B, (+)-(4S,6R)-6-hydroxy-piperitone and (-)-(4R,6S)-6-hydroxy-piperitone. 0.1% Tween 80 and 0.9% DMSO aqueous solution were used as controls. Nicosulfuron (Nic) (0.045 mL / mL) was used as a recommended dose. 2 ) was used as the positive control. Twenty germinated weed seeds were randomly placed in each culture dish, repeated three times. All culture dishes containing seeds were placed in an incubator. After 5 days, the root and shoot lengths of the weed seedlings were measured, and the inhibition rate was calculated according to formula (3):

[0097]

[0098] Table 3 Inhibitory effects of compounds of formula I to IV at a concentration of 300 μg / mL on the germination of three weed seeds (3 days)

[0099]

[0100]

[0101] Table 4 Inhibitory effects of compounds of formula I to IV at a concentration of 300 μg / mL on the growth of three weed seedlings (5 days)

[0102]

[0103] As shown in Tables 3 and 4, the piperitone-type monoterpenoid compounds provided by the present invention have a good inhibitory effect on the seed germination and seedling growth of three weeds: barnyard grass, crabgrass and Amaranthus retroflexus.

[0104] Test Example 2

[0105] Determination of the herbicidal activity of (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV) in combination with other herbicides

[0106] 1. Seed germination test

[0107] The Petri dish method was used, and the specific steps were the same as those described in Test Example 1. M in the sample was (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV), and the concentration was the concentration of (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV) + the concentration of the compound agent. The inhibitory effects on three weed seeds are shown in Table 5:

[0108] Table 5 Inhibitory effects of compound IV in combination with other herbicides on germination of three weed seeds

[0109] Sample Concentration (μg / mL) barnyard grass Crabgrass Amaranthus retroflexus M+2,4-D 100+100 82.31 89.68 90.43 M+Trifluralin 100+100 92.13 97.62 99.26 M+Atrazine 100+100 95.41 97.53 99.12 M+acetochlor 100+100 96.54 100.00 100.00 M+Nicosulfuron 100+100 89.52 93.38 95.67 M+Glufosinate 100+100 86.67 93.06 96.18

[0110] 2. Seedling growth test

[0111] The Petri dish method was used, and the specific steps were the same as those described in Test Example 1. M in the sample was (-)-(4R,6S)-6-hydroxy-piperitone (Formula IV), and the concentration was the concentration of (-)-(4R,6S)-6-hydroxy-piperitone + the concentration of the compound agent. The inhibitory effects on three weed seeds are shown in Table 6:

[0112] Table 6 Inhibitory effect of compound IV in combination with other herbicides on the growth of three weed seedlings

[0113]

[0114]

[0115] As shown in Tables 5 and 6, the combination of the piperitone-type monoterpenoid compound provided by the present invention and other herbicides has a good inhibitory effect on the seed germination and seedling growth of three weeds: barnyard grass, crabgrass and Amaranthus retroflexus.

[0116] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A piperitone-type monoterpenoid compound, characterized in that: It has the structure shown in Formula I or Formula II:

2. The method for preparing the piperitone-type monoterpenoid compound according to claim 1, characterized in that: The following steps are involved: extracting the plant raw material with methanol-water solution and concentrating the extract to obtain an alcohol extract; the plant raw material comprises one or more plants of the genus Murraya, the genus Litsea and the genus Pyrola; The alcohol extract is subjected to a first silica gel column chromatography separation, with petroleum ether, ethyl acetate and methanol as the mobile phases, to obtain petroleum ether, ethyl acetate and methanol elution fractions, respectively; The ethyl acetate elution fraction was subjected to RP-18 reverse phase column chromatography to obtain five fractions A to E after gradient elution; the mobile phase for the gradient elution was methanol / water with a volume ratio of 40:60, 60:40, 80:20, 90:10, and 100:0; Fraction D was subjected to a second silica gel column chromatography separation, and after gradient elution, the same fractions were combined to obtain four fractions D1 to D4; the mobile phase for the gradient elution was petroleum ether / acetone in volume ratios of 10:0, 10:1, 5:1, 3:1, 1:1, and 0:10; The D2 portion was separated by a third silica gel column chromatography, and after elution, the same components were combined into 4 portions D 2-1 ~D 2-4 The mobile phase for elution was petroleum ether / acetone in a volume ratio of 5:1; D 2-3 The fourth silica gel column chromatography was performed to separate the D 2-3-1 and D 2-3-2 part; the elution mobile phase was petroleum ether / acetone with a volume ratio of 5:1; D 2-3-1 and D 2-3-2 The parts were separated and purified by high performance liquid chromatography to obtain the compound of formula I and the compound of formula II respectively; the mobile phase of the high performance liquid chromatography was methanol / water with a volume ratio of 9:

1.

3. The preparation method according to claim 2, characterized in that The plants of the genus Murraya include Murraya oleifera.

4. The preparation method according to claim 2, characterized in that The number of extractions is 3 to 5; the temperature of each extraction is 60 to 80° C., and the time is 1 to 3 hours; the mass ratio of the plant raw material to methanol is 1:3 to 5; and the mass concentration of the methanol aqueous solution is 90 to 95%.

5. The preparation method according to claim 2, characterized in that The particle size of the silica gel in the first, second, third and fourth silica gel column chromatography separations is 200-300 meshes.

6. The preparation method according to claim 2, characterized in that Also includes: D 2-2 The residues were separated and purified by high performance liquid chromatography to obtain compounds of formula III and formula IV; the mobile phase of the high performance liquid chromatography was methanol / water in a volume ratio of 9:1; 7. Use of a piperitone-type monoterpenoid compound or a salt thereof in a herbicide, characterized in that: The piperitone-type monoterpenoid compound has a structure shown in any of the following structural formulas:

8. The use according to claim 7, characterized in that The piperitone-type monoterpenoid compound or its salt is suitable for use on one or more of grass weeds, sedge weeds and broadleaf weeds.

9. The use according to claim 8, characterized in that The weeds include one or more of barnyard grass, crabgrass and Amaranthus retroflexus.

10. A herbicide composition comprising an active ingredient and an adjuvant; characterized in that: The active component is a piperitone-type monoterpenoid compound or a salt thereof; The adjuvant includes one or more of insecticides, fungicides and plant growth regulators; The piperitone-type monoterpenoid compound has a structure shown in any of the following structural formulas:

Images