WO2023179234A1 - Stabilizer-containing fungicidal composition preparation - Google Patents
Stabilizer-containing fungicidal composition preparation Download PDFInfo
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- WO2023179234A1 WO2023179234A1 PCT/CN2023/075337 CN2023075337W WO2023179234A1 WO 2023179234 A1 WO2023179234 A1 WO 2023179234A1 CN 2023075337 W CN2023075337 W CN 2023075337W WO 2023179234 A1 WO2023179234 A1 WO 2023179234A1
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- WIPO (PCT)
- Prior art keywords
- crown
- stabilizer
- composition preparation
- terms
- wetting
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- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000003381 stabilizer Substances 0.000 title claims abstract description 66
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940001468 citrate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- TUTWLYPCGCUWQI-UHFFFAOYSA-N decanamide Chemical compound CCCCCCCCCC(N)=O TUTWLYPCGCUWQI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940050411 fumarate Drugs 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical group NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102220090095 rs1042713 Human genes 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940075554 sorbate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
Definitions
- the invention belongs to the field of pesticide formulation processing and relates to a bactericidal composition preparation containing a stabilizer.
- the active ingredient is a pyrimidinamine fungicide, which was developed by Shenyang Sinochem Pesticide Chemical R&D Co., Ltd. and has independent intellectual property rights.
- This product has good preventive and therapeutic effects on cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, cucumber target spot, wheat powdery mildew, and rapeseed sclerotinia.
- the compound patent is CN106167484 and has been authorized.
- active ingredients are the main ones.
- the specific characteristics of the active ingredients will determine the dosage form of the final preparation. What dosage form it is suitable for and what kind of auxiliaries it matches with will be what needs to be solved at present. There is currently no formula I. Reports on formulation studies related to the indicated compounds.
- the present invention increased the hard water hardness and dilution factor requirements of the corresponding preparation during the research stage.
- the automatic dispersion and dilution stability of ordinary preparation products are tested by diluting 50 times under 342ppm hard water conditions, and the suspension rate is tested by diluting 250 times under 342ppm hard water conditions.
- the detection of automatic dispersibility, dilution stability and suspension rate of the preparation products in the present invention are all completed by diluting 20 times under the condition of 1000 ppm hard water.
- the detection conditions and environment involved in the present invention are much higher than those of ordinary preparations. Compared with ordinary preparations, it is more able to adapt to the characteristics of complex types, large quantities and less water used in aircraft spray tank mixes. Therefore, the composition preparation of the present invention is more practical. meaning of use.
- the object of the present invention is to provide a bactericidal composition formulation containing a stabilizer.
- a fungicidal composition preparation containing a stabilizer containing a stabilizer.
- the active ingredients of the composition preparation include a pyrimidine-containing substituted pyrazole compound and at least one agriculturally acceptable auxiliary agent; wherein the auxiliary agent at least contains a stabilizer; the active ingredient Accounting for 0.1-90% of the mass of the preparation, the stabilizer accounts for 1-20% of the mass of the composition, and the stabilizer is a crown ether compound.
- the substituted pyrazole compound of pyrimidine is a compound represented by formula I;
- R3 is selected from hydrogen, hydroxyl, formyl or C1-C4 alkyl
- R4 and R5 can be the same or different and are respectively selected from hydrogen, halogen or C1-C4 alkyl
- R6 and R7 can be the same or different and are respectively selected from Hydrogen, halogen or C1-C4 alkyl
- R8 and R9 can be the same or different and are respectively selected from hydrogen, cyano, halogen or C1-C4 alkyl
- R11 is selected from halogen, hydroxyl, amino, cyano, nitro or C1- C4 alkyl
- n is selected from an integer from 0 to 5
- R14, R15, R16 or R17 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, amino, cyano, nitro or C1-C4 alkyl
- W is selected from hydrogen, halogen or C1-C4 alkyl
- the general formula I The salts of the compounds shown
- the crown ether compounds are 2-(allyloxymethyl)-18-crown-6-ether, 24-crown-8-ether, 4-nitrobenzene-18-crown-6, 18-crown-5 [4-(2,4-dinitrophenylazo)phenol], N,N'-dibenzyl-4,13-diaza-18-crown 6-ether, 4-tert-butylcyclohexane-15 -Crown-5, 4'-aminobenzo-18-crown-6, benzazepine-15-crown-5, bis(1,4-phenylene)-34-crown-10-ether, 4'- Acetylbenzo-18-crown-6-ether, 4',4”(5”)-di-tert-butyldicyclohexyldicyclohexyl-18-crown-6, 1-fluoro-tetrafluorene, 1,4,7 -Triazacyclononane, 2-aminomethyl-15-crown-5, di
- the dosage form of the preparation is selected from the group consisting of suspensions, dispersible oil suspensions, dispersible oils, emulsifiable concentrates, microemulsions, water emulsions, soluble agents, ultra-low volume agents, water-dispersible granules, water-dispersible tablets, and dry suspensions. , wettable powder, soluble powder, soluble granule, soluble tablet or emulsifiable powder.
- composition preparation is in the form of a suspension dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the thickening rheological agent is 0.1-10%, and the anti-corrosion agent is 0.1-10% agent, 1-15% antifreeze, 0.1-5% defoaming agent, and the rest is water;
- composition preparation is a dispersible oil suspension dosage form
- active ingredients are 0.1-90%
- stabilizer is 1-20%
- wetting and dispersing agent is 0.1-40%
- the thickening rheological agent is 0.1-10 %, the rest is medium;
- composition preparation is a dispersible oil formulation
- the active ingredient is 0.1-90%
- the stabilizer is 1-20%
- the solvent is 1-90%
- the wetting and dispersing agent is 0.1-40%
- the rest is the medium ;
- composition preparation When the composition preparation is in the form of emulsifiable concentrate, the active ingredients are 0.1-90%, the stabilizer is 1-20%, and the balance is solvent in terms of weight percentage;
- composition preparation is a microemulsion dosage form
- active ingredients are 0.1-90%
- stabilizer is 1-20%
- solvent is 1-90%
- wetting and dispersing agent is 0.1-40%
- rest is water
- composition preparation is a water emulsion
- active ingredient is 0.1-90%
- stabilizer is 1-20%
- solvent is 1-90%
- wetting and dispersing agent is 0.1-40%
- rest is water
- composition preparation is a soluble dosage form
- active ingredient is 0.1-90%
- stabilizer is 1-20%
- wetting and dispersing agent is 0.1-40%
- balance is solvent or water
- composition preparation is an ultra-low volume dosage form, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, and the rest is the medium;
- composition preparation is in the form of water-dispersible granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest as a carrier or filler;
- the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as a carrier or filler;
- the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier or filler;
- composition preparation is in the form of wettable powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier; carrier
- composition preparation is in the form of a soluble powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are filler;
- composition preparation is in the form of soluble granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as filler;
- composition preparation is in the form of a soluble tablet, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler ;
- composition preparation is an emulsifiable powder dosage form
- active ingredients are 0.1-90%
- stabilizer is 1-20%
- solvent is 1-90%
- wetting and dispersing agent is 0.1-40%
- defoaming agent is 0.1 -5% and the rest is carrier.
- the wetting and dispersing agents in each of the above preparations are selected from alkyl sulfates, lignosulfonates, naphthalene sulfonates, polycarboxylates, etc.
- the solvent is selected from xylene, mineral spirits S-100, mineral spirits S-150, mineral spirits S-200, cyclohexanone, dimethyl sulfoxide, dimethylformamide, 1 methyl 2 pyrrolidone, octyl pyrrolidone, Decylamide, octylamide, isophorone, methyl carbonate, methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methanol, isopropyl alcohol, n-butanol, polyethylene glycol, methylated vegetable oil, Epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, sec-butyl acetate, liquid paraffin, etc.
- the thickening rheological agent is selected from sodium alginate, xanthan gum, modified xanthan gum, magnesium aluminum silicate, organic bentonite and white carbon black.
- Antifreeze is selected from ethylene glycol, propylene glycol, glycerol, urea and complex phosphates.
- the preservative is selected from sodium benzoate, kason, biological preservatives, etc.
- Defoaming agents are selected from polysiloxanes, polyethers, polyether-modified silicones and high-carbon alcohols.
- the medium is selected from methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methylated vegetable oil, epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, liquid paraffin, etc.
- the carrier is selected from diatomite, kaolin, attapulgite, light calcium carbonate, etc.
- the filler is selected from potassium chloride, potassium sulfate, ammonium sulfate, sodium sulfate, etc.
- the water is distilled water.
- the preparation product can be applied by manual spray or aircraft spray during use.
- the bactericidal composition preparation of the present invention is used in combination with the composition of stabilizers and active ingredients and formula components.
- the sample can improve the performance of the sample in high-concentration hard water (hardness 1000 ppm).
- the self-dispersing property self-dispersing property is higher than 95%), improves the dilution stability and effective suspension rate (effective suspension rate is higher than 95%) under low dilution ratio (20 times dilution) and high hardness hard water conditions.
- the active ingredient is the compound described in formula I, and the structural formula is as follows:
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- W is selected from hydrogen, i.e. compound A.
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-trifluoromethyl
- W is selected from hydrogen, which is compound B;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R15 Br
- W is selected from hydrogen, which is compound C;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R16 NO2
- W is selected from hydrogen, which is compound D;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- W is selected from chlorine, i.e. compound E;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R15 chlorine
- W is selected from hydrogen, which is compound F;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R14 chlorine
- W is selected from hydrogen, that is, compound G;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R15 methoxy group
- W is selected from hydrogen, which is compound H;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- R15 NO2
- W is selected from hydrogen, which is compound I;
- R3 is selected from hydrogen
- R4 and R5 are selected from hydrogen
- R6 and R7 are selected from hydrogen
- R8 and R9 are selected from hydrogen
- R11 is selected from 4-chloro
- n 1
- R14 and R16 are selected from hydrogen
- W selected from hydrogen, that is, compound J.
- Dilution stability Add 5 ml of sample into a 100 ml graduated cylinder filled with 95 ml of high-hardness hard water. Take the middle of the measuring cylinder as the axis. After inverting it 30 times, place it in a constant temperature water bath at 30°C for 24.0 hours, and record the oil/floating oil. and volume of precipitate/precipitate.
- Effective suspension rate The sample mass is increased to 25g (accurate to 0.0001g), the hard water hardness is increased to 1000ppm, and the remaining steps are performed according to GB/T 14825. Transfer the remaining 1/10 of the suspension and sediment to a 50mL volumetric flask, wash all the remaining 25mL into the 50mL volumetric flask with 20mL acetonitrile three times, shake under ultrasonic waves for 5 minutes, return to room temperature, and dilute to volume. Shake well, filter, and measure the mass to calculate the effective suspension rate.
- Process steps Prepare the original drug, stabilizer, auxiliary and water according to the proportion, stir and moisten thoroughly, use high shear dispersant to rough grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size. The samples were tested after being heated for 14 days.
- Process steps Prepare the original drug, stabilizer, additives and medium according to the proportion, stir thoroughly and then use high shear dispersant to coarsely grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size for discharge. , test after 14 days of thermal storage.
- Process steps Prepare the original drug, solvent and medium according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples were tested after 14 days of thermal storage.
- Process steps Prepare the original drug, co-solvent and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples are stored hot for 14 days and tested after expiration.
- Process steps Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, pour distilled water in proportion, stir until completely transparent and discharge. Samples are stored hot for 14 days and tested after expiration.
- Process steps Mix the original drug and solvent according to the proportion, stir until completely transparent, add stabilizer and additives and continue stirring until completely transparent, finally inject distilled water in proportion, and use a high-shear emulsifier to cut until a uniform milky white product is produced. Materials for later use. Samples are stored hot for 14 days and tested after expiration.
- Process steps Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, add distilled water to make up, continue stirring until completely transparent and discharge. The samples are stored hot for 14 days and tested after expiration.
- Process steps Prepare the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use.
- the samples are stored hot for 14 days and tested after expiration.
- Emulsifiable powder is a powder of Emulsifiable powder
- the active ingredient particles or molecules can be fully coated and anchored to form a more stable group, thereby acting as a stabilizer. Therefore, the automatic dispersibility, dilution stability and suspension rate of the stabilizer-containing composition preparation of the present invention were tested under the condition of 1000 ppm hard water and 20 times dilution, and were significantly improved compared to the control example without stabilizer.
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Abstract
The present invention relates to a stabilizer-containing fungicidal composition preparation. The composition can be prepared into products of various dosage forms in combination with necessary formula components. After the product is subjected to an accelerated thermal storage test (54℃, 14d), the automatic dispersity of the sample in high-concentration hard water (hardness: 1000 ppm) can be improved (the automatic dispersity is higher than 95%), and the dilution stability and effective suspension rate under a low dilution ratio (20-time dilution) and high-hardness hard water conditions are increased (the effective suspension rate is higher than 95%).
Description
本发明属于农药剂型加工领域，涉及一种含稳定剂的杀菌组合物制剂。The invention belongs to the field of pesticide formulation processing and relates to a bactericidal composition preparation containing a stabilizer.
有效成分属于嘧啶胺类杀菌剂，由沈阳中化农药化工研发有限公司开发，具有自主知识产权。该产品对黄瓜霜霉病、黄瓜白粉病、黄瓜炭疽病、黄瓜靶斑病、小麦白粉病、油菜菌核病具有较好的预防和治疗效果。化合物专利为CN106167484已获得授权。The active ingredient is a pyrimidinamine fungicide, which was developed by Shenyang Sinochem Pesticide Chemical R&D Co., Ltd. and has independent intellectual property rights. This product has good preventive and therapeutic effects on cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, cucumber target spot, wheat powdery mildew, and rapeseed sclerotinia. The compound patent is CN106167484 and has been authorized.
本行业可知大多数农药的原药不能直接使用，必须加工配制成各种类型的制剂才能使用，因此根据使用方法和作物的不同，要配制成相应的制剂应用，以提高农药生物活性，并减少用药量，降低成本，减少对环境的污染。This industry knows that the original pesticides of most pesticides cannot be used directly and must be processed and formulated into various types of preparations before they can be used. Therefore, according to the use methods and crops, corresponding preparations must be formulated and applied to improve the biological activity of the pesticides and reduce the dosage, reduce costs, and reduce environmental pollution.
但配制制剂时以活性成分为主，活性成分的特定特性将决定其最终形成制剂的剂型，其适合什么剂型以及与怎样的助剂相匹配将是目前所需要解决的，目前并未有式I所示化合物相关制剂研究的报道。However, when formulating preparations, active ingredients are the main ones. The specific characteristics of the active ingredients will determine the dosage form of the final preparation. What dosage form it is suitable for and what kind of auxiliaries it matches with will be what needs to be solved at present. There is currently no formula I. Reports on formulation studies related to the indicated compounds.
为了提高该化合物在不同施用场景的适用性，尤其是能够适应飞机喷雾施药的要求，本发明在研究阶段就提高了相应制剂在硬水硬度和稀释倍数的要求。普通制剂产品的自动分散性和稀释稳定性在342ppm硬水条件下稀释50倍检测，悬浮率在342ppm硬水条件下稀释250倍检测。本发明中制剂产品对于自动分散性、稀释稳定性和悬浮率的检测均在1000ppm硬水的条件下稀释20倍完成。本发明所涉及的检测条件和环境远高于普通制剂产品，相比于普通制剂更加能够适应飞机喷雾桶混药剂种类复杂、数量多、用水少的特点，因此本发明的组合物制剂更具有实际使用意义。In order to improve the applicability of the compound in different application scenarios, especially to adapt to the requirements of aircraft spray application, the present invention increased the hard water hardness and dilution factor requirements of the corresponding preparation during the research stage. The automatic dispersion and dilution stability of ordinary preparation products are tested by diluting 50 times under 342ppm hard water conditions, and the suspension rate is tested by diluting 250 times under 342ppm hard water conditions. The detection of automatic dispersibility, dilution stability and suspension rate of the preparation products in the present invention are all completed by diluting 20 times under the condition of 1000 ppm hard water. The detection conditions and environment involved in the present invention are much higher than those of ordinary preparations. Compared with ordinary preparations, it is more able to adapt to the characteristics of complex types, large quantities and less water used in aircraft spray tank mixes. Therefore, the composition preparation of the present invention is more practical. meaning of use.
发明内容Contents of the invention
本发明的目的是提供一种含稳定剂的杀菌组合物制剂。The object of the present invention is to provide a bactericidal composition formulation containing a stabilizer.
为实现上述目的，本发明的技术方案如下：In order to achieve the above objects, the technical solutions of the present invention are as follows:
一种含稳定剂的杀菌组合物制剂，组合物制剂活性成分含嘧啶的取代吡唑类化合物以及农业上可接受的至少一种助剂；其中，助剂中至少含有稳定剂；所述活性成分占制剂质量的0.1-90％，稳定剂占组合物制剂质量的1-20％，稳定剂为冠醚类化合物。A fungicidal composition preparation containing a stabilizer. The active ingredients of the composition preparation include a pyrimidine-containing substituted pyrazole compound and at least one agriculturally acceptable auxiliary agent; wherein the auxiliary agent at least contains a stabilizer; the active ingredient Accounting for 0.1-90% of the mass of the preparation, the stabilizer accounts for 1-20% of the mass of the composition, and the stabilizer is a crown ether compound.
所述嘧啶的取代吡唑类化合物为式Ⅰ所示的化合物；
The substituted pyrazole compound of pyrimidine is a compound represented by formula I;
The substituted pyrazole compound of pyrimidine is a compound represented by formula I;
式中，R3选自氢、羟基、甲酰基或C1-C4烷基；R4、R5可相同或不同，分别选自氢、卤素或C1-C4烷基；R6、R7可相同或不同分别选自氢、卤素或C1-C4烷基；R8、R9可相同或不同分别选自氢、氰基、卤素或C1-C4烷基；R11选自卤素、羟基、氨基、氰基、硝基或C1-C4烷基；n选自0至5的整数，R14、
R15、R16或R17可相同或不同分别选自氢、卤素、羟基、氨基、氰基、硝基或C1-C4烷基；W选自氢、卤素或C1-C4烷基；所述通式I所示化合物的盐为通式化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、草酸、甲磺酸、对甲苯磺酸、苯甲酸、邻苯二甲酸、马来酸、富马酸、山梨酸、苹果酸或柠檬酸形成的盐。In the formula, R3 is selected from hydrogen, hydroxyl, formyl or C1-C4 alkyl; R4 and R5 can be the same or different and are respectively selected from hydrogen, halogen or C1-C4 alkyl; R6 and R7 can be the same or different and are respectively selected from Hydrogen, halogen or C1-C4 alkyl; R8 and R9 can be the same or different and are respectively selected from hydrogen, cyano, halogen or C1-C4 alkyl; R11 is selected from halogen, hydroxyl, amino, cyano, nitro or C1- C4 alkyl; n is selected from an integer from 0 to 5, R14, R15, R16 or R17 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, amino, cyano, nitro or C1-C4 alkyl; W is selected from hydrogen, halogen or C1-C4 alkyl; the general formula I The salts of the compounds shown are compounds of the general formula and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid , sorbic acid, malic acid or citric acid salts.
所述冠醚类化合物为2-(烯丙氧基甲基)-18-冠-6-醚、24-冠8-醚、4-硝基苯-18-冠-6、18-冠-5[4-(2,4-二硝基苯偶氮)苯酚]、N,N'-二苄基-4,13-二氮杂-18-冠6-醚、4-叔丁基环己烷-15-冠-5、4'-氨基苯并-18-冠醚-6、苯杂氮-15-冠-5、双(1,4-亚苯基)-34-冠10-醚、4'-乙酰苯并-18-冠-6-醚、4',4”(5”)-二叔丁基二环己基并-18-冠-6、1-氟-四氟烯、1,4,7-三氮杂环壬烷、2-氨基甲基-15-冠-5、二环己烷并-18-冠醚-6、2-(羟甲基)-15-冠5-醚、二环己烷并-24-冠醚-8、2-羟甲基-12-冠-4、聚(二苯并-18-冠-6)、18-冠醚-6、1,4,7-三甲基-1,4,7-三氮杂环壬烷、环己烷-18-冠-6、1-氮杂-12-冠4-醚、1,5,9-三氮杂环十二烷、苯并-12-冠-4、1-氮杂-15-冠-5-醚、1-氮杂-18-冠-6-醚中的一种或几种联合使用。The crown ether compounds are 2-(allyloxymethyl)-18-crown-6-ether, 24-crown-8-ether, 4-nitrobenzene-18-crown-6, 18-crown-5 [4-(2,4-dinitrophenylazo)phenol], N,N'-dibenzyl-4,13-diaza-18-crown 6-ether, 4-tert-butylcyclohexane-15 -Crown-5, 4'-aminobenzo-18-crown-6, benzazepine-15-crown-5, bis(1,4-phenylene)-34-crown-10-ether, 4'- Acetylbenzo-18-crown-6-ether, 4',4”(5”)-di-tert-butyldicyclohexyldicyclohexyl-18-crown-6, 1-fluoro-tetrafluorene, 1,4,7 -Triazacyclononane, 2-aminomethyl-15-crown-5, dicyclohexano-18-crown-6, 2-(hydroxymethyl)-15-crown-5-ether, bicyclo Hexano-24-crown-8, 2-hydroxymethyl-12-crown-4, poly(dibenzo-18-crown-6), 18-crown-6, 1,4,7-tri Methyl-1,4,7-triazacyclononane, cyclohexane-18-crown-6, 1-aza-12-crown 4-ether, 1,5,9-triazacyclododecane One or more of alkane, benzo-12-crown-4, 1-aza-15-crown-5-ether, and 1-aza-18-crown-6-ether are used in combination.
所述制剂剂型选自悬浮剂、可分散油悬浮剂、可分散油剂、乳油、微乳剂、水乳剂、可溶液剂、超低容量剂、水分散粒剂、水分散片剂、干悬浮剂、可湿性粉剂、可溶粉剂、可溶粒剂、可溶片剂或可乳化粉剂。The dosage form of the preparation is selected from the group consisting of suspensions, dispersible oil suspensions, dispersible oils, emulsifiable concentrates, microemulsions, water emulsions, soluble agents, ultra-low volume agents, water-dispersible granules, water-dispersible tablets, and dry suspensions. , wettable powder, soluble powder, soluble granule, soluble tablet or emulsifiable powder.
所述组合物制剂为悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，增稠流变剂0.1-10％，防腐剂0.1-10％，抗冻剂1-15％，消泡剂0.1-5％，其余为水；When the composition preparation is in the form of a suspension dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the thickening rheological agent is 0.1-10%, and the anti-corrosion agent is 0.1-10% agent, 1-15% antifreeze, 0.1-5% defoaming agent, and the rest is water;
所述组合物制剂为可分散油悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，增稠流变剂0.1-10％，其余为介质；When the composition preparation is a dispersible oil suspension dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, and the thickening rheological agent is 0.1-10 %, the rest is medium;
所述组合物制剂为可分散油剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为介质；When the composition preparation is a dispersible oil formulation, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is the medium ;
所述组合物制剂为乳油剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，余量为溶剂；When the composition preparation is in the form of emulsifiable concentrate, the active ingredients are 0.1-90%, the stabilizer is 1-20%, and the balance is solvent in terms of weight percentage;
所述组合物制剂为微乳剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为水；When the composition preparation is a microemulsion dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is water;
所述组合物制剂为水乳剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为水；When the composition preparation is a water emulsion, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is water;
所述组合物制剂为可溶液剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，余量为溶剂或水；When the composition preparation is a soluble dosage form, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, and the balance is solvent or water;
所述组合物制剂为超低容量剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，其余为介质；When the composition preparation is an ultra-low volume dosage form, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, and the rest is the medium;
所述组合物制剂为水分散粒剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition preparation is in the form of water-dispersible granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest as a carrier or filler;
所述组合物制剂为水分散片剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition is in the form of a water-dispersible tablet, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as a carrier or filler;
所述组合物制剂为干悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition is in the form of a dry suspension, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier or filler;
所述组合物制剂为可湿性粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体；When the composition preparation is in the form of wettable powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier; carrier
所述组合物制剂为可溶粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；
When the composition preparation is in the form of a soluble powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are filler;
所述组合物制剂为可溶粒剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；When the composition preparation is in the form of soluble granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as filler;
所述组合物制剂为可溶片剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；When the composition preparation is in the form of a soluble tablet, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler ;
所述组合物制剂为可乳化粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体。When the composition preparation is an emulsifiable powder dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the defoaming agent is 0.1 -5% and the rest is carrier.
上述各制剂中润湿分散剂选自烷基硫酸盐、木质素磺酸盐、萘磺酸盐、聚羧酸盐等。The wetting and dispersing agents in each of the above preparations are selected from alkyl sulfates, lignosulfonates, naphthalene sulfonates, polycarboxylates, etc.
溶剂选自二甲苯、溶剂油S-100、溶剂油S-150、溶剂油S-200、环己酮、二甲基亚砜、二甲基甲酰胺、1甲基2吡咯烷酮、辛基吡咯烷酮、癸酰胺、辛酰胺、异佛尔酮、碳酸甲酯、油酸甲酯、松脂油、C2-C18脂肪酸甲酯、甲醇、异丙醇、正丁醇、聚乙二醇、甲基化植物油、环氧大豆油、菜籽油、棉籽油、松节油、乙二醇单丁醚、丙二醇单甲醚、乙酸仲丁酯、液体石蜡等。The solvent is selected from xylene, mineral spirits S-100, mineral spirits S-150, mineral spirits S-200, cyclohexanone, dimethyl sulfoxide, dimethylformamide, 1 methyl 2 pyrrolidone, octyl pyrrolidone, Decylamide, octylamide, isophorone, methyl carbonate, methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methanol, isopropyl alcohol, n-butanol, polyethylene glycol, methylated vegetable oil, Epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, sec-butyl acetate, liquid paraffin, etc.
增稠流变剂选自海藻酸钠、黄原胶、改性黄原胶、硅酸镁铝、有机膨润土和白炭黑等。The thickening rheological agent is selected from sodium alginate, xanthan gum, modified xanthan gum, magnesium aluminum silicate, organic bentonite and white carbon black.
抗冻剂选自乙二醇、丙二醇、丙三醇、尿素和复合磷酸盐类等。Antifreeze is selected from ethylene glycol, propylene glycol, glycerol, urea and complex phosphates.
防腐剂选自苯甲酸钠、卡松、生物防腐剂等。The preservative is selected from sodium benzoate, kason, biological preservatives, etc.
消泡剂选自聚硅氧烷类、聚醚类、聚醚改性硅类和高碳醇类等。Defoaming agents are selected from polysiloxanes, polyethers, polyether-modified silicones and high-carbon alcohols.
介质选自油酸甲酯、松脂油、C2-C18脂肪酸甲酯、甲基化植物油、环氧大豆油、菜籽油、棉籽油、松节油、液体石蜡等。The medium is selected from methyl oleate, rosin oil, C2-C18 fatty acid methyl ester, methylated vegetable oil, epoxidized soybean oil, rapeseed oil, cottonseed oil, turpentine, liquid paraffin, etc.
载体选自硅藻土、高岭土、凹凸棒土、轻质碳酸钙等。The carrier is selected from diatomite, kaolin, attapulgite, light calcium carbonate, etc.
填料选自氯化钾、硫酸钾、硫酸铵、硫酸钠等。The filler is selected from potassium chloride, potassium sulfate, ammonium sulfate, sodium sulfate, etc.
所述水为蒸馏水。The water is distilled water.
所述制剂产品在使用过程中可采用人工喷雾和飞机喷雾的施药方式。The preparation product can be applied by manual spray or aircraft spray during use.
本发明所具有的优点：Advantages of the present invention:
本发明杀菌组合物制剂通过稳定剂和有效成分的组合物与配方组分的联合使用，所得制剂产品经过热储加速实验(54℃，14d)后，可提高样品在高浓度硬水(硬度1000ppm)中的自动分散性(自动分散性高于95％)，提高低稀释倍数(20倍稀释)和高硬度硬水条件下的稀释稳定性和有效悬浮率(有效悬浮率高于95％)。The bactericidal composition preparation of the present invention is used in combination with the composition of stabilizers and active ingredients and formula components. After the obtained preparation product undergoes a thermal storage acceleration test (54°C, 14d), the sample can improve the performance of the sample in high-concentration hard water (hardness 1000 ppm). The self-dispersing property (self-dispersing property is higher than 95%), improves the dilution stability and effective suspension rate (effective suspension rate is higher than 95%) under low dilution ratio (20 times dilution) and high hardness hard water conditions.
下面结合具体实施例来对本发明进行进一步说明，但并不将本发明局限于这些具体实施方式。本发明涵盖了权利要求书范围内所可能包括的所有备选方案、改进方案和等效方案。实施例中的原药及其余各物料均有市售。The present invention will be further described below with reference to specific examples, but the present invention is not limited to these specific implementations. The present invention covers all alternatives, improvements and equivalents that may be included within the scope of the claims. The original drugs and other materials in the examples are all commercially available.
下述各实施例中活性成分为式I所述化合物，结构式如下：
In the following examples, the active ingredient is the compound described in formula I, and the structural formula is as follows:
In the following examples, the active ingredient is the compound described in formula I, and the structural formula is as follows:
具体化合物物：Specific compounds:
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R15、R16或R17分别选自氢，W选自氢，即化合物A。R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are selected from Hydrogen, W is selected from hydrogen, i.e. compound A.
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-三氟甲基，n＝1，R14、R15、R16或R17分别选自氢，W选自氢，即为化合物B；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-trifluoromethyl, n=1, R14, R15, R16 or R17 are respectively selected from hydrogen, and W is selected from hydrogen, which is compound B;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R16、R17分别选自氢，R15＝Br，W选自氢，，即为化合物C；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16 and R17 are selected from hydrogen, R15=Br, W is selected from hydrogen, which is compound C;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R15、R17分别选自氢，R16＝NO2，W选自氢，，即为化合物D；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15 and R17 are selected from hydrogen, R16=NO2, W is selected from hydrogen, which is compound D;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R15、R16或R17分别选自氢，W选自氯，即化合物E；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R15, R16 or R17 are selected from Hydrogen, W is selected from chlorine, i.e. compound E;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R16、R17分别选自氢，R15＝氯，W选自氢，即为化合物F；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16 and R17 are selected from hydrogen, R15=chlorine, W is selected from hydrogen, which is compound F;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R15、R16、R17分别选自氢，R14＝氯，W选自氢，即化合物G；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R15, R16 and R17 are selected from hydrogen, R14 = chlorine, W is selected from hydrogen, that is, compound G;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R16、R17分别选自氢，R15＝甲氧基，W选自氢，即为化合物H；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16 and R17 are selected from hydrogen, R15 = methoxy group, W is selected from hydrogen, which is compound H;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R16、R17分别选自氢，R15＝NO2，W选自氢，即为化合物I；R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14, R16 and R17 are selected from hydrogen, R15=NO2, W is selected from hydrogen, which is compound I;
R3选自氢，R4、R5分别选自氢，R6、R7分别选自氢，R8、R9分别选自氢，R11选自4-氯，n＝1，R14、R16选自氢，R15、R17选自氯，W选自氢，即化合物J。R3 is selected from hydrogen, R4 and R5 are selected from hydrogen, R6 and R7 are selected from hydrogen, R8 and R9 are selected from hydrogen, R11 is selected from 4-chloro, n=1, R14 and R16 are selected from hydrogen, R15 and R17 Selected from chlorine, W selected from hydrogen, that is, compound J.
上述具体化合物分别于乙酸乙酯中，室温搅拌下与浓盐酸反应即形成相应化合物的盐酸盐、硫酸盐、磷酸盐、甲酸盐、乙酸盐、三氟乙酸盐、草酸盐、甲磺酸盐、对甲苯磺酸盐、苯甲酸盐、邻苯二甲酸盐、马来酸盐、富马酸盐、山梨酸盐、苹果酸盐或柠檬酸盐。The above specific compounds are reacted with concentrated hydrochloric acid in ethyl acetate respectively under room temperature stirring to form hydrochloride, sulfate, phosphate, formate, acetate, trifluoroacetate, oxalate, etc. of the corresponding compounds. Mesylate, p-toluenesulfonate, benzoate, phthalate, maleate, fumarate, sorbate, malate or citrate.
实验方法：每个实施例和对照例按照配方比例和工艺制备样品，制备过程均按照常规制剂制备过程进行操作。按照GB/T 19136-2003中“液体制剂”、“粉体制剂”和“其它制剂”进行热储稳定性试验，在(54±2)℃的恒温箱中放置14天。热储14天后，测定有效成分自动分散性、待试样品在20倍稀释和1000ppm硬水条件下的有效悬浮率和稀释稳定性。所有实施例中制剂配比中百分含量均为重量百分比。Experimental methods: For each example and comparative example, samples were prepared according to the formula proportions and processes, and the preparation process was carried out according to the conventional preparation preparation process. Conduct thermal storage stability tests in accordance with "liquid preparations", "powder preparations" and "other preparations" in GB/T 19136-2003, and place them in a constant temperature oven at (54±2)°C for 14 days. After 14 days of thermal storage, the automatic dispersibility of the active ingredients, the effective suspension rate and dilution stability of the sample to be tested under 20-fold dilution and 1000 ppm hard water conditions were measured. The percentages in the preparation ratios in all examples are weight percentages.
自动分散性测试方法：Automatic dispersion test method:
将测试用的高硬度硬水(硬度1000ppm)、量筒和待试样品在测试前平衡至所需温度。测定待试样品密度，计算相当于12.5ml样品的质量(c)，在所需温
度下将237.5ml高硬度硬水注入量筒，放在天平上，在量筒顶上1㎝处加入计量的制剂，15s内完全加完。Equilibrate the high-hardness hard water (hardness 1000ppm), measuring cylinder and sample to be tested to the required temperature before testing. Determine the density of the sample to be tested and calculate the mass (c) equivalent to 12.5ml of the sample at the required temperature. Pour 237.5ml of high-hardness hard water into the measuring cylinder at a certain temperature, place it on the balance, add the measured preparation 1 cm above the top of the measuring cylinder, and complete the addition within 15 seconds.
加完待试样品后立即塞住量筒，翻转一次，在无振动及热源的条件下静置5min±10s,小心去塞，在10-15s内抽去上部225ml悬浮液，保证管尖始终在页面下1㎝处，使对悬浮液的干扰最小。利用液相色谱法检测留在量筒中25±1ml悬浮液的有效成分质量(Q)，从而计算待试样品的自动分散性。
Immediately after adding the sample to be tested, plug the measuring cylinder, turn it over once, let it stand for 5 minutes ± 10 seconds without vibration and heat source, remove the plug carefully, and remove the upper 225ml of suspension within 10-15 seconds, ensuring that the tip of the tube is always in place. 1cm below the page to minimize interference with the suspension. Use liquid chromatography to detect the mass (Q) of the active ingredient remaining in the 25±1ml suspension in the graduated cylinder to calculate the automatic dispersibility of the sample to be tested.
Immediately after adding the sample to be tested, plug the measuring cylinder, turn it over once, let it stand for 5 minutes ± 10 seconds without vibration and heat source, remove the plug carefully, and remove the upper 225ml of suspension within 10-15 seconds, ensuring that the tip of the tube is always in place. 1cm below the page to minimize interference with the suspension. Use liquid chromatography to detect the mass (Q) of the active ingredient remaining in the 25±1ml suspension in the graduated cylinder to calculate the automatic dispersibility of the sample to be tested.
低稀释倍数(20倍稀释)和高硬度硬水条件下，稀释稳定性和有效悬浮率测试方法：Test methods for dilution stability and effective suspension rate under low dilution ratio (20 times dilution) and high hardness hard water conditions:
稀释稳定性：将5ml试样加入装有95ml高硬度硬水的100ml量筒中，以量筒中部为轴心，上下颠倒30次后，放置于30℃恒温水浴中24.0h，记录其浮油/浮膏和沉淀/析出物的体积。Dilution stability: Add 5 ml of sample into a 100 ml graduated cylinder filled with 95 ml of high-hardness hard water. Take the middle of the measuring cylinder as the axis. After inverting it 30 times, place it in a constant temperature water bath at 30°C for 24.0 hours, and record the oil/floating oil. and volume of precipitate/precipitate.
有效悬浮率：试样质量提高至25g(精确至0.0001g)，硬水硬度提高至1000ppm，其余步骤按GB/T 14825操作进行。将剩余的1/10悬浮液及沉淀物转移至50mL容量瓶中，用20mL乙腈分3次将25mL的剩余物全部洗入50mL容量瓶中，在超声波下振荡5min,恢复至室温，定容，摇匀，过滤后，测定质量计算其有效悬浮率。Effective suspension rate: The sample mass is increased to 25g (accurate to 0.0001g), the hard water hardness is increased to 1000ppm, and the remaining steps are performed according to GB/T 14825. Transfer the remaining 1/10 of the suspension and sediment to a 50mL volumetric flask, wash all the remaining 25mL into the 50mL volumetric flask with 20mL acetonitrile three times, shake under ultrasonic waves for 5 minutes, return to room temperature, and dilute to volume. Shake well, filter, and measure the mass to calculate the effective suspension rate.
悬浮剂：Suspending agent:
工艺步骤：将原药、稳定剂、助剂和水按照比例进行配制，充分搅拌润湿后利用高剪切分散剂进行粗磨打浆，然后将浆料注入砂磨机砂磨至合适粒径出料，所得样品热储14天后进行检测。
Process steps: Prepare the original drug, stabilizer, auxiliary and water according to the proportion, stir and moisten thoroughly, use high shear dispersant to rough grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size. The samples were tested after being heated for 14 days.
Process steps: Prepare the original drug, stabilizer, auxiliary and water according to the proportion, stir and moisten thoroughly, use high shear dispersant to rough grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size. The samples were tested after being heated for 14 days.
可分散油悬浮剂dispersible oil suspension
工艺步骤：将原药、稳定剂、助剂和介质按照比例进行配制，充分搅拌均匀后利用高剪切分散剂进行粗磨打浆，然后将浆料注入砂磨机砂磨至合适粒径出料，热储14天后进行检测。
Process steps: Prepare the original drug, stabilizer, additives and medium according to the proportion, stir thoroughly and then use high shear dispersant to coarsely grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size for discharge. , test after 14 days of thermal storage.
Process steps: Prepare the original drug, stabilizer, additives and medium according to the proportion, stir thoroughly and then use high shear dispersant to coarsely grind and slurry, then inject the slurry into the sand mill and sand it to a suitable particle size for discharge. , test after 14 days of thermal storage.
可分散油剂：Dispersible oil:
工艺步骤：将原药、溶剂和介质按照比例进行配制，搅拌至完全溶解，加入稳定剂和助剂继续搅拌溶解至完全透明，出料备用。样品热储14天后进行检测。
Process steps: Prepare the original drug, solvent and medium according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples were tested after 14 days of thermal storage.
Process steps: Prepare the original drug, solvent and medium according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples were tested after 14 days of thermal storage.
乳油：Cream:
工艺步骤：将原药、助溶剂和溶剂按照比例进行配制，搅拌至完全溶解，加入稳定剂和助剂继续搅拌溶解至完全透明，出料备用。样品热储14天，到期后检测。
Process steps: Prepare the original drug, co-solvent and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples are stored hot for 14 days and tested after expiration.
Process steps: Prepare the original drug, co-solvent and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. Samples are stored hot for 14 days and tested after expiration.
微乳剂：Microemulsion:
工艺步骤：将原药和溶剂按照比例进行混合，搅拌至完全溶解，加入稳定剂和助剂继续搅拌至完全透明，最后按比例将蒸馏水注入，搅拌至完全透明出料备用。样品热储14天，到期后检测
Process steps: Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, pour distilled water in proportion, stir until completely transparent and discharge. Samples are stored hot for 14 days and tested after expiration.
Process steps: Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, pour distilled water in proportion, stir until completely transparent and discharge. Samples are stored hot for 14 days and tested after expiration.
水乳剂：Water emulsion:
工艺步骤：将原药和溶剂按照比例进行混合，搅拌至完全透明，加入稳定剂和助剂继续搅拌至完全透明，最后按比例将蒸馏水注入，用高剪切乳化机剪切至均匀乳白色产品出料备用。样品热储14天，到期后检测。
Process steps: Mix the original drug and solvent according to the proportion, stir until completely transparent, add stabilizer and additives and continue stirring until completely transparent, finally inject distilled water in proportion, and use a high-shear emulsifier to cut until a uniform milky white product is produced. Materials for later use. Samples are stored hot for 14 days and tested after expiration.
Process steps: Mix the original drug and solvent according to the proportion, stir until completely transparent, add stabilizer and additives and continue stirring until completely transparent, finally inject distilled water in proportion, and use a high-shear emulsifier to cut until a uniform milky white product is produced. Materials for later use. Samples are stored hot for 14 days and tested after expiration.
可溶液剂：Soluble agents:
工艺步骤：将原药和溶剂按照比例进行混合，搅拌至完全溶解，加入稳定剂和助剂继续搅拌至完全透明，最后用蒸馏水补足，继续搅拌至完全透明出料备用。样品热储14天，到期后进行检测。
Process steps: Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, add distilled water to make up, continue stirring until completely transparent and discharge. The samples are stored hot for 14 days and tested after expiration.
Process steps: Mix the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives and continue stirring until completely transparent. Finally, add distilled water to make up, continue stirring until completely transparent and discharge. The samples are stored hot for 14 days and tested after expiration.
超低容量剂：Ultra low volume agent:
工艺步骤：将原药和溶剂按照比例进行配制，搅拌至完全溶解，加入稳定剂和助剂继续搅拌溶解至完全透明，出料备用。样品热储14天，到期后进行检测。
Process steps: Prepare the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. The samples are stored hot for 14 days and tested after expiration.
Process steps: Prepare the original drug and solvent according to the proportion, stir until completely dissolved, add stabilizer and additives, continue stirring and dissolving until completely transparent, and discharge the material for later use. The samples are stored hot for 14 days and tested after expiration.
水分散粒剂：Water dispersible granules:
将原药、助剂、稳定剂和介质按照比例充分混合，再利用气流/超微粉碎机进行粉碎，将粉体物料加水捏合，然后利用水平圆盘/双螺杆造粒机进行挤压造粒，所得物料烘干后备用。样品热储14天，到期后检测。
Fully mix the original drug, additives, stabilizers and media according to the proportion, then use an airflow/ultrafine pulverizer to crush, add water to the powder material and knead it, and then use a horizontal disc/twin-screw granulator for extrusion granulation. , the obtained material is dried and ready for use. Samples are stored hot for 14 days and tested after expiration.
Fully mix the original drug, additives, stabilizers and media according to the proportion, then use an airflow/ultrafine pulverizer to crush, add water to the powder material and knead it, and then use a horizontal disc/twin-screw granulator for extrusion granulation. , the obtained material is dried and ready for use. Samples are stored hot for 14 days and tested after expiration.
水分散片剂：Water dispersible tablets:
将原药、助剂、稳定剂和介质按照比例充分混合，再利用气流/超微粉碎机进行粉碎，将粉体物料经压片机进行打片，所得物料样品热储14天，到期后检测。
Fully mix the original drug, additives, stabilizers and media according to the proportion, and then use an airflow/ultrafine pulverizer to crush the powder material into tablets through a tablet press. The resulting material sample is stored hot for 14 days. After expiration detection.
Fully mix the original drug, additives, stabilizers and media according to the proportion, and then use an airflow/ultrafine pulverizer to crush the powder material into tablets through a tablet press. The resulting material sample is stored hot for 14 days. After expiration detection.
干悬浮剂：Dry suspension agent:
将原药、助剂和水充分混合后，利用高剪切分散机进行分散打浆，然后利用砂磨机砂磨成合适粘度和粒径的浆料。将浆料利用喷雾干燥装置干燥成固体颗粒产品。所得物料热储14天，到期后检测。
After fully mixing the original drug, additives and water, use a high shear disperser to disperse and beat, and then use a sand mill to grind it into a slurry with appropriate viscosity and particle size. The slurry is dried into solid granular products using a spray drying device. The resulting material is stored hot for 14 days and tested after expiration.
After fully mixing the original drug, additives and water, use a high shear disperser to disperse and beat, and then use a sand mill to grind it into a slurry with appropriate viscosity and particle size. The slurry is dried into solid granular products using a spray drying device. The resulting material is stored hot for 14 days and tested after expiration.
可湿性粉剂：
Wettable powder:
将原药、稳定剂、助剂和介质按照比例进行配制，利用混合机进行充分混合，然后利用气流或超微粉碎机进行物料粉碎。所得物料热储14天，到期后检测。
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The resulting material is stored hot for 14 days and tested after expiration.
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The resulting material is stored hot for 14 days and tested after expiration.
可溶粉剂：Soluble powder:
将原药、稳定剂、助剂和介质按照比例进行配制，利用混合机进行充分混合，然后利用气流或超微粉碎机进行物料粉碎。所得物料热储14天，到期后检测。
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The resulting material is stored hot for 14 days and tested after expiration.
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The resulting material is stored hot for 14 days and tested after expiration.
可溶粒剂：Soluble granules:
将原药、稳定剂、助剂和介质按照比例进行配制，利用混合机进行充分混合，然后利用气流或超微粉碎机进行物料粉碎。再将粉料经水平圆盘或螺杆挤压造粒机制备成颗粒状物料，烘干后所得物料热储14天，到期后进行检测。
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The powder is then prepared into granular materials through a horizontal disc or screw extrusion granulator. After drying, the resulting material is stored hot for 14 days and tested after expiration.
Prepare the original drug, stabilizer, auxiliary agent and medium according to the proportion, use a mixer to mix thoroughly, and then use an air flow or ultra-fine pulverizer to crush the material. The powder is then prepared into granular materials through a horizontal disc or screw extrusion granulator. After drying, the resulting material is stored hot for 14 days and tested after expiration.
可乳化粉剂：Emulsifiable powder:
将原药、稳定剂和部分助剂溶解在溶剂中，利用白炭黑进行吸附，所得粉体物料与其余助剂及填料进行混合，混合后经气流或超微粉碎后所得物料，热储14天后检测指标。
Dissolve the original drug, stabilizer and some additives in the solvent, use white carbon black for adsorption, and mix the resulting powder material with the remaining additives and fillers. After mixing, the resulting material is pulverized by air flow or ultrafine, and the heat storage is 14 Diva detection indicators.
Dissolve the original drug, stabilizer and some additives in the solvent, use white carbon black for adsorption, and mix the resulting powder material with the remaining additives and fillers. After mixing, the resulting material is pulverized by air flow or ultrafine, and the heat storage is 14 Diva detection indicators.
综上所述：由于冠醚类化合物结构特性，可以将有效成分颗粒或分子进行充分的包覆和锚定形成更加稳定的基团，从而起到稳定剂的作用。因此，本发明含稳定剂的组合物制剂在1000ppm硬水，稀释20倍条件下检测自动分散性、稀释稳定性和悬浮率，相比不加稳定剂的对照例有明显的提高。
To sum up: due to the structural characteristics of crown ether compounds, the active ingredient particles or molecules can be fully coated and anchored to form a more stable group, thereby acting as a stabilizer. Therefore, the automatic dispersibility, dilution stability and suspension rate of the stabilizer-containing composition preparation of the present invention were tested under the condition of 1000 ppm hard water and 20 times dilution, and were significantly improved compared to the control example without stabilizer.
Claims (5)
- 一种含稳定剂的杀菌组合物制剂，其特征在于：组合物制剂活性成分含嘧啶的取代吡唑类化合物以及农业上可接受的至少一种助剂；其中，助剂中至少含有稳定剂；所述活性成分占制剂质量的0.1-90％，稳定剂占组合物制剂质量的1-20％，稳定剂为冠醚类化合物。A fungicidal composition preparation containing a stabilizer, characterized in that: the active ingredients of the composition preparation include a pyrimidine-containing substituted pyrazole compound and at least one agriculturally acceptable auxiliary; wherein the auxiliary contains at least a stabilizer; The active ingredient accounts for 0.1-90% of the mass of the preparation, the stabilizer accounts for 1-20% of the mass of the composition, and the stabilizer is a crown ether compound.
- 根据权利要求1含稳定剂的杀菌组合物制剂，其特征在于：所述嘧啶的取代吡唑类化合物为式Ⅰ所示的化合物；
The fungicidal composition preparation containing a stabilizer according to claim 1, characterized in that: the substituted pyrazole compound of the pyrimidine is a compound represented by formula I;
式中，R3选自氢、羟基、甲酰基或C1-C4烷基；R4、R5可相同或不同，分别选自氢、卤素或C1-C4烷基；R6、R7可相同或不同分别选自氢、卤素或C1-C4烷基；R8、R9可相同或不同分别选自氢、氰基、卤素或C1-C4烷基；R11选自卤素、羟基、氨基、氰基、硝基或C1-C4烷基；n选自0至5的整数，R14、R15、R16或R17可相同或不同分别选自氢、卤素、羟基、氨基、氰基、硝基或C1-C4烷基；W选自氢、卤素或C1-C4烷基；所述通式I所示化合物的盐为通式化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、草酸、甲磺酸、对甲苯磺酸、苯甲酸、邻苯二甲酸、马来酸、富马酸、山梨酸、苹果酸或柠檬酸形成的盐。In the formula, R3 is selected from hydrogen, hydroxyl, formyl or C1-C4 alkyl; R4 and R5 can be the same or different and are respectively selected from hydrogen, halogen or C1-C4 alkyl; R6 and R7 can be the same or different and are respectively selected from Hydrogen, halogen or C1-C4 alkyl; R8 and R9 can be the same or different and are respectively selected from hydrogen, cyano, halogen or C1-C4 alkyl; R11 is selected from halogen, hydroxyl, amino, cyano, nitro or C1- C4 alkyl; n is selected from an integer from 0 to 5, R14, R15, R16 or R17 can be the same or different and are respectively selected from hydrogen, halogen, hydroxyl, amino, cyano, nitro or C1-C4 alkyl; W is selected from Hydrogen, halogen or C1-C4 alkyl; the salt of the compound represented by the general formula I is a compound of the general formula and hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, Salts formed from benzoic acid, phthalic acid, maleic acid, fumaric acid, sorbic acid, malic acid or citric acid. - 根据权利要求1含稳定剂的杀菌组合物制剂，其特征在于：所述冠醚类化合物为2-(烯丙氧基甲基)-18-冠-6-醚、24-冠8-醚、4-硝基苯-18-冠-6、18-冠-5[4-(2,4-二硝基苯偶氮)苯酚]、N,N'-二苄基-4,13-二氮杂-18-冠6-醚、4-叔丁基环己烷-15-冠-5、4'-氨基苯并-18-冠醚-6、苯杂氮-15-冠-5、双(1,4-亚苯基)-34-冠10-醚、4'-乙酰苯并-18-冠-6-醚、4',4”(5”)-二叔丁基二环己基并-18-冠-6、1-氟-四氟烯、1,4,7-三氮杂环壬烷、2-氨基甲基-15-冠-5、二环己烷并-18-冠醚-6、2-(羟甲基)-15-冠5-醚、二环己烷并-24-冠醚-8、2-羟甲基-12-冠-4、聚(二苯并-18-冠-6)、18-冠醚-6、1,4,7-三甲基-1,4,7-三氮杂环壬烷、环己烷-18-冠-6、1-氮杂-12-冠4-醚、1,5,9-三氮杂环十二烷、苯并-12-冠-4、1-氮杂-15-冠-5-醚、1-氮杂-18-冠-6-醚中的一种或几种联合使用。The bactericidal composition preparation containing a stabilizer according to claim 1, characterized in that: the crown ether compound is 2-(allyloxymethyl)-18-crown-6-ether, 24-crown-8-ether, 4-nitrobenzene-18-crown-6, 18-crown-5[4-(2,4-dinitrophenylazo)phenol], N,N'-dibenzyl-4,13-diazo Hetero-18-crown-6-ether, 4-tert-butylcyclohexane-15-crown-5, 4'-aminobenzo-18-crown-6, benzazepine-15-crown-5, bis(1, 4-phenylene)-34-crown-10-ether, 4'-acetylbenzo-18-crown-6-ether, 4',4”(5”)-di-tert-butyldicyclohexyl-18- Crown-6, 1-fluoro-tetrafluorene, 1,4,7-triazacyclononane, 2-aminomethyl-15-crown-5, dicyclohexano-18-crown-6, 2-(hydroxymethyl)-15-crown-5-ether, dicyclohexano-24-crown-8, 2-hydroxymethyl-12-crown-4, poly(dibenzo-18-crown- 6), 18-crown-6, 1,4,7-trimethyl-1,4,7-triazacyclononane, cyclohexane-18-crown-6, 1-aza-12- Crown-4-ether, 1,5,9-triazacyclododecane, benzo-12-crown-4, 1-aza-15-crown-5-ether, 1-aza-18-crown- One or more of the 6-ethers are used in combination.
- 根据权利要求1含稳定剂的杀菌组合物制剂，其特征在于：所述制剂剂型选自悬浮剂、可分散油悬浮剂、可分散油剂、乳油、微乳剂、水乳剂、可溶液剂、超低容量剂、水分散粒剂、水分散片剂、干悬浮剂、可湿性粉剂、可溶粉剂、可溶粒剂、可溶片剂或可乳化粉剂。The bactericidal composition preparation containing a stabilizer according to claim 1, characterized in that: the preparation dosage form is selected from the group consisting of suspensions, dispersible oil suspensions, dispersible oils, emulsifiable concentrates, microemulsions, aqueous emulsions, solubilizers, super Low volume agent, water-dispersible granule, water-dispersible tablet, dry suspension, wettable powder, soluble powder, soluble granule, soluble tablet or emulsifiable powder.
- 根据权利要求1-4任意一项含稳定剂的杀菌组合物制剂，其特征在于：所述组合物制剂为悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，增稠流变剂0.1-10％，防腐剂0.1-10％，抗冻剂1-15％，消泡剂0.1-5％，其余为水； The bactericidal composition preparation containing a stabilizer according to any one of claims 1 to 4, characterized in that: when the composition preparation is a suspension dosage form, the active ingredient is 0.1-90% and the stabilizer is 1-20% by weight. %, wetting and dispersing agent 0.1-40%, thickening rheology agent 0.1-10%, preservative 0.1-10%, antifreeze 1-15%, defoaming agent 0.1-5%, the rest is water;所述组合物制剂为可分散油悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，增稠流变剂0.1-10％，其余为介质；When the composition preparation is a dispersible oil suspension dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, and the thickening rheological agent is 0.1-10 %, the rest is medium;所述组合物制剂为可分散油剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为介质；When the composition preparation is a dispersible oil formulation, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is the medium ;所述组合物制剂为乳油剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，余量为溶剂；When the composition preparation is in the form of emulsifiable concentrate, the active ingredients are 0.1-90%, the stabilizer is 1-20%, and the balance is solvent in terms of weight percentage;所述组合物制剂为微乳剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为水；When the composition preparation is a microemulsion dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is water;所述组合物制剂为水乳剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，其余为水；When the composition preparation is a water emulsion, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the rest is water;所述组合物制剂为可溶液剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，余量为溶剂或水；When the composition preparation is a soluble dosage form, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, and the balance is solvent or water;所述组合物制剂为超低容量剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，其余为介质；When the composition preparation is an ultra-low volume dosage form, in terms of weight percentage, the active ingredient is 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, and the rest is the medium;所述组合物制剂为水分散粒剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition preparation is in the form of water-dispersible granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest as a carrier or filler;所述组合物制剂为水分散片剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition is in the form of a water-dispersible tablet, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as a carrier or filler;所述组合物制剂为干悬浮剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体或填料；When the composition is in the form of a dry suspension, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier or filler;所述组合物制剂为可湿性粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体；When the composition preparation is in the form of wettable powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are carrier; carrier所述组合物制剂为可溶粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；When the composition preparation is in the form of a soluble powder, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizers are 1-20%, the wetting and dispersing agents are 0.1-40%, the defoaming agents are 0.1-5%, and the rest are filler;所述组合物制剂为可溶粒剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；When the composition preparation is in the form of soluble granules, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest as filler;所述组合物制剂为可溶片剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为填料；When the composition preparation is in the form of a soluble tablet, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the wetting and dispersing agent is 0.1-40%, the defoaming agent is 0.1-5%, and the rest is filler ;所述组合物制剂为可乳化粉剂剂型时，按重量百分比计，有效成分0.1-90％，稳定剂1-20％，溶剂1-90％，润湿分散剂0.1-40％，消泡剂0.1-5％，其余为载体。 When the composition preparation is an emulsifiable powder dosage form, in terms of weight percentage, the active ingredients are 0.1-90%, the stabilizer is 1-20%, the solvent is 1-90%, the wetting and dispersing agent is 0.1-40%, and the defoaming agent is 0.1 -5% and the rest is carrier.
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| CN202210291336.2A CN116831116A (en) | 2022-03-23 | 2022-03-23 | Sterilizing composition preparation containing stabilizer |
| CN202210291336.2 | 2022-03-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010180187A (en) * | 2009-02-09 | 2010-08-19 | Kureha Corp | Crown ether derivative, method for producing the same and insecticide containing the same |
| CN106167484A (en) * | 2015-05-18 | 2016-11-30 | 沈阳中化农药化工研发有限公司 | Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use |
| CN106889073A (en) * | 2015-12-17 | 2017-06-27 | 沈阳中化农药化工研发有限公司 | A kind of sterilized, Insecticiding-miticiding preparation |
| CN108684681A (en) * | 2017-03-31 | 2018-10-23 | 沈阳中化农药化工研发有限公司 | A kind of mite-killing preparation and its application |
-
2022
- 2022-03-23 CN CN202210291336.2A patent/CN116831116A/en active Pending
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- 2023-02-10 WO PCT/CN2023/075337 patent/WO2023179234A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010180187A (en) * | 2009-02-09 | 2010-08-19 | Kureha Corp | Crown ether derivative, method for producing the same and insecticide containing the same |
| CN106167484A (en) * | 2015-05-18 | 2016-11-30 | 沈阳中化农药化工研发有限公司 | Substituted pyrazolecarboxylic compounds containing pyrimidine and its production and use |
| CN106889073A (en) * | 2015-12-17 | 2017-06-27 | 沈阳中化农药化工研发有限公司 | A kind of sterilized, Insecticiding-miticiding preparation |
| CN108684681A (en) * | 2017-03-31 | 2018-10-23 | 沈阳中化农药化工研发有限公司 | A kind of mite-killing preparation and its application |
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