A 5-aminolevulinic acid ester, use and pesticide composition

Abstract

The present invention provides a 5-aminolevulinic acid ester, use and pesticide composition, wherein the 5-aminolevulinic acid ester is formed by condensing three 5-ALAs with 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 present invention develops a compound structure with pesticide drugability based on 5-ALA, provides a specific preparation method of the structure, and also provides an implementation scheme for the application of the compound in pesticides, overcoming the disadvantages of 5-ALA having poor stability and fat solubility and requiring a large concentration to kill pests and diseases, and the technical scheme is suitable for industrial production.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide preparation, and more specifically, to a 5-aminolevulinic acid ester, use and pesticide composition. Background Art

[0002] 5-Aminolevulinic acid (5-ALA) is an endogenous biological substance and a precursor for the biosynthesis of animal hemoglobin and plant chlorophyll. It is widely used in the medical field and can be used as a photosensitizer for the treatment of various cancers. The earliest report on its application in the field of pesticides was found in the Chicago Bulletin in the United States. A certain concentration of 5-ALA under light can effectively kill field weeds. In addition, it can cause convulsions and death to various pests such as flies and cockroaches. Subsequently, many documents have reported on its photooxidation effect to kill pests and diseases, but no pesticides containing 5-ALA have been marketed.

[0003] After research, it was found that the fundamental reason is that 5-ALA has poor stability and fat solubility, and requires a higher concentration to kill pests and diseases. However, 5-ALA is relatively expensive and difficult to use on a large scale, and is not worth preparing pesticides. Summary of the invention

[0004] In view of the above-mentioned defects and problems in the prior art, the present invention provides a 5-aminolevulinic acid ester, use and pesticide composition.

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

[0006] A 5-aminolevulinic acid ester, the structural formula of which is:

[0007]

[0008] The 5-aminolevulinic acid ester is prepared by condensing three 5-ALA with 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.

[0009] In the above technical solution, the 5-aminolevulinic acid ester is hydrochloride, sulfate, or phosphate.

[0010] In the above technical solution, when R1 is methyl and forms a hydrochloride, a compound 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) is formed, and its structural formula is:

[0011]

[0012] The invention discloses a use of 5-aminolevulinic acid ester. When the 5-aminolevulinic acid ester is used in a relatively low dosage, test data show that the dosage can reach as low as 80ug / ml, and the 5-aminolevulinic acid ester is suitable for killing a variety of pests and diseases, including rice sheath blight, wheat fusarium head blight, corn leaf blight, rapeseed sclerotinia, tomato gray mold, grape white rot, melon anthracnose, apple ring rot, citrus green mold, potato late blight, flies, cockroaches and the like.

[0013] The invention discloses a pesticide composition comprising 5-aminolevulinic acid ester, comprising the aminolevulinic acid ester and fluthiazolinone in a weight ratio of 1:60 to 60:15;

[0014] The preparation method comprises the following steps:

[0015] (1) Weighing each component according to the stated weight parts;

[0016] (2) The components are mixed and stirred evenly to prepare various pesticide formulations.

[0017] In the above technical solution, the sum of the weights of the active ingredients of the pesticide composition, 5-aminolevulinic acid ester and fluthiazolinone, accounts for 1%-90% of the total weight of the composition, and the rest is the pesticide carrier.

[0018] In the above technical solution, the pesticide carrier is selected from any one of emulsifiers, solvents, dispersants, disintegrants, thickeners, preservatives, stabilizers, antifreeze agents, defoamers, fillers, binders, dyes or water, or a mixture of more than one of them in any proportion.

[0019] In the above technical scheme, the pesticide formulation includes any one of emulsifiable concentrate, suspension, wettable powder, water dispersible granule, aqueous emulsion, microemulsion, seed treatment agent, paste or aerosol. The methods for preparing these pesticide formulations are well known to those skilled in the art.

[0020] In the above technical scheme, the emulsifier is any one of calcium dodecylbenzene 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, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether or alkylphenol formaldehyde resin polyoxyethylene ether, or a mixture thereof in any ratio; the solvent is any one of xylene, biodiesel, toluene, diesel, methanol, ethanol, ethylene glycol, n-butanol, isopropanol, turpentine, solvent oil, dimethylformamide, dimethyl sulfoxide or water, or a mixture thereof in any ratio.

[0021] In the above technical scheme, the dispersant is one or more of polycarboxylates, lignin sulfonates, alkylphenol polyoxyethylene ether formaldehyde condensates, calcium dodecylbenzene sulfonate, naphthalenesulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene ether, 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, alkylbenzene sulfonate calcium, naphthalenesulfonate, pull open powder BX, wetting penetrant F, tristyrylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, triphenylphenol polyoxyethylene ether phosphate, saponin powder, silkworm feces or soapberry powder; the disintegrant 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.

[0022] In the above technical scheme, the preservative is one or more of formaldehyde, benzoic acid or sodium benzoate; the stabilizer is sodium citrate or resorcinol; the antifreeze 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 alcohols; the filler is one or more of kaolin, diatomaceous earth, bentonite, attapulgite, white carbon black, starch or light calcium carbonate.

[0023] In the above technical scheme, the binder is one or more of polysaccharide polymer compounds, polypropylene graft copolymers, xanthan gum, microbial mucilage, cellulose derivatives, sodium carboxymethyl cellulose, ethyl cellulose, seaweed, agar, rosin, paraffin, gelatin, pectin, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyacrylamide, polyvinyl pyrrolidone and water-soluble synthetic products of polyol polymers, inorganic binders, clay, water glass or gypsum; the dye is one of rose red, fuchsine, scarlet yellow, blue and purple; the water is any of distilled water, softened water, natural water or deionized water.

[0024] The invention also discloses the use of the pesticide composition, which is suitable for preparing medicines for preventing and killing nematode diseases of rice, vegetables and fruit trees.

[0025] The present invention develops a compound structure with pesticide drugability based on 5-ALA, provides a specific preparation method for the structure, and also provides an implementation plan for the use of the compound in pesticides, thereby overcoming the disadvantages of 5-ALA having poor stability and fat solubility and requiring a higher concentration to kill pests and diseases. The technical solution is suitable for industrial production. DETAILED DESCRIPTION

[0026] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] An example of a 5-aminolevulinic acid ester compound shown as an example is as follows:

[0028] Example 1. Synthesis of 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) hydrochloride

[0029] Add 1000ml of methanol to the reaction vessel, add 10g of 2-methylpropanetriol and 16g of 5-aminolevulinic acid under stirring, heat to 60℃ and stir evenly, slowly add 20ml of concentrated sulfuric acid, keep warm for 2 hours, concentrate to a small volume, add 600ml of dichloromethane to dissolve, add 500ml of water and stir quickly for 20 minutes, separate the dichloromethane layer, add 300g of anhydrous magnesium sulfate, stir for 30 minutes, let stand overnight. Filter, take the filtrate, add 30ml of concentrated hydrochloric acid under stirring, stir for 2 hours, adjust the pH value to neutral with sodium hydroxide, concentrate to a small volume, crystallize and dry to obtain 13g of 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester).

[0030] Example 2: Preparation of pesticide composition suspension

[0031] Weigh the following components: 1 kg of 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) hydrochloride, 32 kg of fluthiazolin, 1 kg of sodium alkyl sulfonate, 4 kg of sodium salt of alkylnaphthalenesulfonic acid polycondensate, 0.2 kg of xanthan gum, 4 kg of ethylene glycol, and 56.8 kg of water; use water as a medium, add the remaining components into a sand mill, grind them into a suspension concentrate of 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) hydrochloride and fluthiazolin.

[0032] Example 3: Preparation of aqueous dispersant of pesticide composition

[0033] The components are weighed according to the following weights: 5 kg of 2-methylpropane-1,2,3-tris(5-aminolevulinate) hydrochloride, 15 kg of fluthiazolin, 10 kg of sodium naphthalenesulfonate formaldehyde condensate, 3 kg of sodium n-butylnaphthalenesulfonate, and 77 kg of kaolin; the original drug, powdered carrier, and wetting dispersant are mixed and crushed, and then water is added and kneaded, and then added into a granulator for granulation, and then dried and sieved (according to the range of the sieve) to obtain a water-dispersible granule prepared by mixing 2-methylpropane-1,2,3-tris(5-aminolevulinate) hydrochloride and fluthiazolin.

[0034] Example 44. Table of control effects of fluthiamethoxam alone and the pesticide combination on dry-pointed nematodes

[0035] Nematode mortality rate = nematode mortality rate / number of tested nematodes × 100%

[0036]

[0037]

[0038] From the above results, it can be seen that the addition of 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) hydrochloride can effectively improve the control effect of fluthiazolinone on nematodes and effectively reduce the amount of fluthiazolinone used.

[0039] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A 5-aminolevulinic acid ester, characterized in that: Its structural formula is: The 5-aminolevulinic acid ester is prepared by condensing three 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.

2. A 5-aminolevulinic acid ester according to claim 1, characterized in that: When R1 is methyl and forms a hydrochloride, a compound 2-methylpropane-1,2,3-tris(5-aminolevulinic acid ester) is formed, and its structural formula is:

3. A use of a 5-aminolevulinic acid ester, characterized in that: The 5-aminolevulinic acid ester described in claim 1 or 2 is used to kill any one of the pests and diseases such as rice sheath blight, wheat fusarium rust, corn leaf blight, rapeseed sclerotinia, tomato gray mold, grape white rot, melon anthracnose, apple ring rot, citrus green mold, potato late blight, flies and cockroaches.

4. A pesticide composition containing 5-aminolevulinic acid ester, characterized in that: A pesticide composition containing the 5-aminolevulinic acid ester according to claim 1 or 2, wherein the weight ratio of the 5-aminolevulinic acid ester to fluthiazolinone is 1:60-60:15; The preparation method comprises the following steps: (1) Weighing each component according to the stated weight parts; (2) The components are mixed and stirred evenly to prepare various pesticide formulations.

5. A pesticide composition containing 5-aminolevulinic acid ester, characterized in that: The pesticide composition contains the 5-aminolevulinic acid ester of claim 1 or 2 and fluthiazolinone, the sum of which accounts for 1% to 90% of the total weight of the composition, and the rest is the pesticide carrier; The pesticide carrier is selected from any one of emulsifiers, solvents, dispersants, disintegrants, thickeners, preservatives, stabilizers, antifreeze agents, defoamers, fillers, binders, dyes or water, or a mixture of more than one of them in any proportion; The pesticide formulation is selected from any one of emulsifiable concentrate, suspension concentrate, wettable powder, water dispersible granules, aqueous emulsion, microemulsion, seed treatment agent, paste or aerosol; The emulsifier is any one of calcium dodecylbenzene 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, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether or alkylphenol formaldehyde resin polyoxyethylene ether, or a mixture of several of them in any ratio; The solvent is one or a mixture of any of the above in any ratio among xylene, biodiesel, toluene, diesel, methanol, ethanol, ethylene glycol, n-butanol, isopropanol, turpentine, solvent oil, dimethylformamide, dimethyl sulfoxide or water; The dispersant is one or more of polycarboxylates, lignin sulfonates, alkylphenol polyoxyethylene ether formaldehyde condensates, calcium dodecylbenzene sulfonate, naphthalenesulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene ether, 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, alkylbenzene calcium sulfonate, naphthalenesulfonate, pull-opening powder BX, wetting penetrant F, tristyrylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, triphenylphenol polyoxyethylene ether phosphate, saponin powder, silkworm feces or soapberry powder; The disintegrant 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; The preservative is one or more of formaldehyde, benzoic acid or sodium benzoate; the stabilizer is sodium citrate or resorcinol; the antifreeze is one or more of ethylene glycol, propylene glycol, glycerol, urea or inorganic salts; the defoamer is one or more of silicone oil, silicone compounds, C10-20 saturated fatty acid compounds or C8-10 fatty alcohols; the filler is one or more of kaolin, diatomaceous earth, bentonite, attapulgite, white carbon black, starch or light calcium carbonate; The binder is one or more of polysaccharide polymer compounds, polypropylene graft copolymers, xanthan gum, microbial mucilage, cellulose derivatives, sodium carboxymethyl cellulose, ethyl cellulose, seaweed, agar, rosin, paraffin, gelatin, pectin, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyacrylamide, polyvinyl pyrrolidone and water-soluble synthetic products of polyol polymers, inorganic binders, clay, water glass or gypsum; the dye is one of rose red, fuchsin, scarlet yellow, blue and purple; the water is any of distilled water, softened water, natural water or deionized water.

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