CN113620828A - 5-aminolevulinic acid ester, application and pesticide composition - Google Patents
5-aminolevulinic acid ester, application and pesticide composition Download PDFInfo
- Publication number
- CN113620828A CN113620828A CN202110945130.2A CN202110945130A CN113620828A CN 113620828 A CN113620828 A CN 113620828A CN 202110945130 A CN202110945130 A CN 202110945130A CN 113620828 A CN113620828 A CN 113620828A
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- CN
- China
- Prior art keywords
- acid ester
- polyoxyethylene ether
- aminolevulinic acid
- water
- pesticide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/22—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated the carbon skeleton being further substituted by oxygen atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
Abstract
The invention provides a 5-aminolevulinic acid ester, application and a pesticide composition, wherein the 5-aminolevulinic acid ester is prepared by condensing 3 5-ALA and corresponding glycerol derivatives through concentrated sulfuric acid, wherein R1 is one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and neopentyl. The invention develops a compound structure with pesticide property by taking 5-ALA as a basic structure, provides a specific preparation mode of the structure, and also provides an embodiment of the compound applied in pesticide, thereby overcoming the defects that the 5-ALA has poor stability and fat solubility and can kill plant diseases and insect pests only by needing larger concentration, and the technical scheme is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of pesticide preparation, in particular to a 5-aminolevulinic acid ester, application and a pesticide composition.
Background
5-aminolevulinic acid (5-ALA) is a biological endogenous substance, is a precursor substance for biosynthesis of animal hemoglobin and phytoalexin, is widely applied to the field of medicines, can be used as a photosensitizer for treating various cancers, is first reported in Chicago communications in the United states in the field of pesticides, can effectively kill weeds in the field by 5-ALA with a certain concentration under illumination, causes spasm and death of various pests such as flies and cockroaches in addition to the phenomenon, and is also reported in a plurality of documents for killing pests by photooxidation, but the 5-ALA-containing pesticides are not available in the market.
The research shows that the fundamental reason is that 5-ALA has poor stability and fat solubility, and needs a larger concentration to kill the plant diseases and insect pests, while 5-ALA has higher price, is difficult to use in a large range and has no value for preparing pesticides.
Disclosure of Invention
In view of the above-mentioned drawbacks and problems of the prior art, the present invention provides a 5-aminolevulinic acid ester, use thereof, and a pesticidal composition.
In order to achieve the purpose, the invention provides the following technical scheme:
a5-aminolevulinic acid ester has a structural formula as follows:
the 5-aminolevulinic acid esterified ester is prepared by condensing 3 5-ALAs and corresponding glycerol derivatives through concentrated sulfuric acid, wherein R1 is one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and neopentyl.
In the technical scheme, the 5-aminolevulinic acid ester is hydrochloride, sulfate and phosphate.
In the above technical scheme, when R1 is methyl and forms hydrochloride, a compound 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) is formed, and the structural formula thereof is:
the invention discloses an application of 5-aminoketone valerate, and test data show that the usage can reach 80ug/ml at least under the condition of lower usage amount of the 5-aminoketone valerate, and the 5-aminoketone valerate is suitable for killing various plant diseases and insect pests, wherein the plant diseases and insect pests comprise rice sheath blight bacteria, wheat scab bacteria, corn microsporum, sclerotinia sclerotiorum, tomato botrytis cinerea, grape white rot bacteria, melon anthracnose bacteria, apple ring rot bacteria, citrus green mold bacteria, potato late blight bacteria, fly and cockroach.
The invention discloses a pesticide composition containing 5-aminolevulinic acid ester, which comprises aminolevulinic acid ester and fluensulfone in a weight ratio of 1: 60-60: 15;
the preparation method comprises the following steps:
(1) weighing the components in parts by weight;
(2) mixing the components, stirring uniformly, and preparing into various pesticide formulations.
In the technical scheme, the sum of the weight of the 5-aminolevulinic acid ester and the fluensulfone serving as the active ingredients of the pesticide composition accounts for 1-90 percent of the total weight of the composition, and the balance is a pesticide carrier.
In the technical scheme, the pesticide carrier is selected from any one or a mixture of more than one of emulsifier, solvent, dispersant, disintegrant, thickener, preservative, stabilizer, antifreeze, defoamer, filler, binder, dye or water in any proportion.
In the technical scheme, the pesticide formulation comprises any one of missible oil, a suspending agent, wettable powder, water dispersible granules, an aqueous emulsion, a microemulsion, a seed treatment agent, an ointment or an aerosol. Wherein methods of preparing such pesticide dosage forms are well known to those of ordinary skill in the art.
In the technical scheme, the emulsifier is one or a mixture of more of calcium dodecyl benzene sulfonate, fatty acid polyoxyethylene ether, alkylphenol polyoxyethylene ether, sulfosuccinate, styrylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene fatty alcohol ether, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether or alkylphenol formaldehyde resin polyoxyethylene ether in any ratio; the solvent is one or a mixture of more of dimethylbenzene, biodiesel, toluene, diesel oil, methanol, ethanol, ethylene glycol, n-butanol, isopropanol, turpentine, solvent oil, dimethylformamide, dimethyl sulfoxide or water in any ratio.
In the technical scheme, the dispersing agent is one or more of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, calcium dodecylbenzene sulfonate, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester, fatty amine polyoxyethylene ether or glycerin fatty acid ester polyoxyethylene ether; the wetting agent is one or more of alkyl sodium sulfate, calcium alkyl benzene sulfonate, naphthalene sulfonate, nekal BX, wetting penetrant F, tristyrylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, tristyrylphenol polyoxyethylene ether phosphate, saponin powder, silkworm excrement or soapberry powder; the disintegrating agent is one or more of bentonite, urea, ammonium sulfate, aluminum chloride, citric acid, succinic acid or sodium bicarbonate; the thickener is one or more of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, magnesium aluminum silicate or polyvinyl alcohol.
In the technical scheme, the preservative is one or more of formaldehyde, benzoic acid or sodium benzoate; the stabilizer is sodium citrate or resorcinol; the antifreezing agent is one or more of ethylene glycol, propylene glycol, glycerol, urea or inorganic salts; the defoaming agent is one or more of silicone oil, silicone compounds, C10-20 saturated fatty acid compounds or C8-10 fatty alcohol; the filler is one or more of kaolin, diatomite, bentonite, attapulgite, white carbon black, starch or light calcium carbonate.
In the technical scheme, the binder is one or more of polysaccharide high molecular compound, polypropylene graft copolymer, xanthan gum, microbial mucilage, cellulose derivative, sodium carboxymethyl cellulose, ethyl cellulose, seaweed, agar, rosin, paraffin, gelatin, pectin, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone, polyalcohol polymer water-soluble synthetic product, inorganic binder, clay, water glass or gypsum; the dye is one of rose bengal, fuchsine, scarlet yellow, blue and purple; the water is any one of distilled water, softened water, natural water or deionized water.
The invention also discloses the application of the pesticide composition, which is suitable for preparing medicines for preventing and killing nematode diseases of paddy rice, vegetables and fruit trees.
The invention develops a compound structure with pesticide property by taking 5-ALA as a basic structure, provides a specific preparation mode of the structure, and also provides an embodiment of the compound applied in pesticide, thereby overcoming the defects that the 5-ALA has poor stability and fat solubility and can kill plant diseases and insect pests only by needing larger concentration, and the technical scheme is suitable for industrial production.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An example of a 5-aminolevulinic acid ester as shown in the examples is as follows:
EXAMPLE 1 Synthesis of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride
Adding 1000ml of methanol into a reaction container, adding 10g of 2-methyl glycerol and 16g of 5-aminolevulinic acid under stirring, heating to 60 ℃, uniformly stirring, slowly dropwise adding 20ml of concentrated sulfuric acid, preserving heat for 2 hours, concentrating to a small volume, adding 600ml of dichloromethane, dissolving, adding 500ml of water, rapidly stirring for 20 minutes, separating a dichloromethane layer, adding 300g of anhydrous magnesium sulfate, stirring for 30 minutes, and standing overnight. Filtering, taking the filtrate, dropwise adding 30ml of concentrated hydrochloric acid while stirring, stirring for 2 hours, adjusting the pH value to be neutral by using sodium hydroxide, concentrating to be small in volume, and carrying out crystallization and drying to obtain 13g of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester).
EXAMPLE 2 preparation of suspension of pesticidal composition
Weighing the following components in parts by weight: 1Kg of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride, 32Kg of fluensulfone, 1Kg of alkyl sodium sulfonate, 4Kg of alkyl naphthalene sulfonic acid polycondensate sodium salt, 0.2Kg of xanthan gum, 4Kg of ethylene glycol and 56.8Kg of water; adding the rest components into a sand grinding kettle by taking water as a medium, and grinding to prepare the suspension compounded by the 2-methylpropane-1, 2, 3-tri (5-aminolevulinic acid ester) hydrochloride and the fluensulfone.
Example 3 preparation of aqueous Dispersion of agricultural chemical composition
Weighing the following components in parts by weight: 5Kg of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride, 15Kg of fluensulfone, 10Kg of sodium naphthalene sulfonate formaldehyde condensate, 3Kg of n-butyl sodium naphthalene sulfonate and 77Kg of kaolin; mixing and crushing the original medicine, the powdery carrier and the wetting dispersant, adding water for kneading, adding into a granulator for granulation, and then drying and screening (according to the range of a screen) to obtain the water dispersible granule compounded by the 2-methylpropane-1, 2, 3-tri (5-aminolevulinic acid ester) hydrochloride and the fluensulfone.
Example 44 Fluthiamethoxam sulfone alone and pesticidal composition for use in control of Aphelenchoides terniformis
Nematode mortality rate ═ nematode mortality rate/number of nematode tested × 100%
From the results, the 2-methyl propane-1, 2, 3-tri (5-aminolevulinic acid ester) hydrochloride is added, so that the control effect of the fluensulfone on the nematodes can be effectively improved, and the use amount of the fluensulfone is effectively reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A5-aminolevulinic acid ester compound characterized in that: the structural formula is as follows:
the 5-aminolevulinic acid esterified ester is prepared by condensing 3 5-ALAs and corresponding glycerol derivatives through concentrated sulfuric acid, wherein R1 is one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and neopentyl.
2. The esterified 5-aminolevulinic acid ester according to claim 1, wherein:
when R1 is methyl and forms hydrochloride, a compound 2-methylpropane-1, 2, 3-tri (5-aminolevulinic acid ester) is formed, and the structural formula is as follows:
3. the use of 5-aminolevulinic acid for esterification is characterized in that: use of a 5-aminolevulinic acid ester according to claims 1-2 for the control of a plurality of plant diseases and insect pests, including rhizoctonia solani, fusarium graminearum, cercospora zeae, sclerotinia sclerotiorum, botrytis cinerea, colletotrichum viniferum, colletotrichum cucurbitacearum, pyricularia malorum, phythora citrea, potatophyte blight, fly, cockroach.
4. A pesticide composition containing 5-aminolevulinic acid ester, which is characterized in that: comprising the 5-aminolevulinic acid ester as defined in claims 1 and 2, the pesticidal composition comprises the 5-aminolevulinic acid ester and fluensulfone in a weight ratio of from 1:60 to 60: 15;
the preparation method comprises the following steps:
(1) weighing the components in parts by weight;
(2) mixing the components, stirring uniformly, and preparing into various pesticide formulations.
5. A pesticide composition containing 5-aminolevulinic acid ester, which is characterized in that: the total weight of the 5-aminolevulinic acid ester and the fluensulfone which are the effective components of the pesticide composition accounts for 1 to 90 percent of the total weight of the composition, and the balance is a pesticide carrier;
the pesticide carrier is selected from any one or a mixture of more than one of emulsifier, solvent, dispersant, disintegrant, thickener, preservative, stabilizer, antifreeze, defoamer, filler, binder, dye or water in any proportion;
the pesticide formulation comprises any one of missible oil, a suspending agent, wettable powder, water dispersible granules, an aqueous emulsion, a microemulsion, a seed treatment agent, an ointment or an aerosol;
the emulsifier is one or a mixture of more of calcium dodecyl benzene sulfonate, fatty acid polyoxyethylene ether, alkylphenol polyoxyethylene ether, sulfosuccinate, styrylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, polyoxyethylene fatty alcohol ether, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether or alkylphenol formaldehyde resin polyoxyethylene ether in any ratio;
the solvent is one or a mixture of more of dimethylbenzene, biodiesel, methylbenzene, diesel oil, methanol, ethanol, ethylene glycol, n-butanol, isopropanol, turpentine, solvent oil, dimethylformamide, dimethyl sulfoxide or water in any ratio;
the dispersing agent is one or more of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, calcium dodecylbenzene sulfonate, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester, fatty amine polyoxyethylene ether or glycerol fatty acid ester polyoxyethylene ether; the wetting agent is one or more of alkyl sodium sulfate, calcium alkyl benzene sulfonate, naphthalene sulfonate, nekal BX, wetting penetrant F, tristyrylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, tristyrylphenol polyoxyethylene ether phosphate, saponin powder, silkworm excrement or soapberry powder;
the disintegrating agent is one or more of bentonite, urea, ammonium sulfate, aluminum chloride, citric acid, succinic acid or sodium bicarbonate;
the thickening agent is one or more of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, magnesium aluminum silicate or polyvinyl alcohol;
the preservative is one or more of formaldehyde, benzoic acid or sodium benzoate; the stabilizer is sodium citrate or resorcinol; the antifreezing agent is one or more of ethylene glycol, propylene glycol, glycerol, urea or inorganic salts; the defoaming agent is one or more of silicone oil, silicone compounds, C10-20 saturated fatty acid compounds or C8-10 fatty alcohol; the filler is one or more of kaolin, diatomite, bentonite, attapulgite, white carbon black, starch or light calcium carbonate;
the binder is one or more of polysaccharide high molecular compound, polypropylene graft copolymer, xanthan gum, microbial mucilage, cellulose derivative, sodium carboxymethylcellulose, ethyl cellulose, seaweed, agar, rosin, paraffin, gelatin, pectin, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone, polyalcohol polymer water-soluble synthetic product, inorganic binder, clay, water glass or gypsum; the dye is one of rose bengal, fuchsine, scarlet yellow, blue and purple; the water is any one of distilled water, softened water, natural water or deionized water.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110945130.2A CN113620828A (en) | 2021-08-17 | 2021-08-17 | 5-aminolevulinic acid ester, application and pesticide composition |
| PCT/CN2021/139308 WO2023019838A1 (en) | 2021-08-17 | 2021-12-17 | 5-aminolevulinic acid ester, use and pesticide composition |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110945130.2A CN113620828A (en) | 2021-08-17 | 2021-08-17 | 5-aminolevulinic acid ester, application and pesticide composition |
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| CN113620828A true CN113620828A (en) | 2021-11-09 |
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| CN202110945130.2A Pending CN113620828A (en) | 2021-08-17 | 2021-08-17 | 5-aminolevulinic acid ester, application and pesticide composition |
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| WO (1) | WO2023019838A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023019838A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | 5-aminolevulinic acid ester, use and pesticide composition |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087225A (en) * | 1992-11-26 | 1994-06-01 | 西北大学 | A kind of prescription of novel photo-activation pesticide powder |
| DE10312659A1 (en) * | 2003-03-21 | 2004-10-07 | Universität Regensburg | New 5-aminolevulinic acid derivatives useful for photodynamic tumor therapy and/or diagnosis |
| GB0700580D0 (en) * | 2007-01-11 | 2007-02-21 | Photocure Asa | Use |
| WO2009077960A1 (en) * | 2007-12-14 | 2009-06-25 | Photoderma Sa | Novel compounds useful in therapeutic and cosmetic methods |
| JP2015199758A (en) * | 2015-06-15 | 2015-11-12 | 住友化学株式会社 | Composition for agricultural chemicals and method for promoting plant growth |
| CN112010772A (en) * | 2016-01-26 | 2020-12-01 | 赵鸣 | Salt compound of 5-aminolevulinic acid and derivative thereof and application |
| CN106083706B (en) * | 2016-06-03 | 2018-04-20 | 浙江工商大学 | Dendrimers and its preparation method and purposes containing 5 aminolevulinic acids and 3 Hydroxypyridinones |
| CL2016003379A1 (en) * | 2016-12-29 | 2017-08-04 | Univ Santiago Chile | "Composition comprising delta-aminolevulinic acid (wing) or a derivative thereof and oxyanions and tellurium or its derivatives and their use for pathogen control." |
| CN113651708A (en) * | 2021-08-17 | 2021-11-16 | 湖南复瑞生物医药技术有限责任公司 | Preparation and post-treatment method of 5-aminolevulinic acid ester |
| CN113620828A (en) * | 2021-08-17 | 2021-11-09 | 湖南复瑞生物医药技术有限责任公司 | 5-aminolevulinic acid ester, application and pesticide composition |
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2021
- 2021-08-17 CN CN202110945130.2A patent/CN113620828A/en active Pending
- 2021-12-17 WO PCT/CN2021/139308 patent/WO2023019838A1/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023019838A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | 5-aminolevulinic acid ester, use and pesticide composition |
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| WO2023019838A1 (en) | 2023-02-23 |
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