CN102816122A - Preparation method of pyrimethanil - Google Patents
Preparation method of pyrimethanil Download PDFInfo
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- CN102816122A CN102816122A CN2012103016197A CN201210301619A CN102816122A CN 102816122 A CN102816122 A CN 102816122A CN 2012103016197 A CN2012103016197 A CN 2012103016197A CN 201210301619 A CN201210301619 A CN 201210301619A CN 102816122 A CN102816122 A CN 102816122A
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- mould amine
- phonetic mould
- cyanamide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- ZLIBICFPKPWGIZ-UHFFFAOYSA-N pyrimethanil Chemical compound CC1=CC(C)=NC(NC=2C=CC=CC=2)=N1 ZLIBICFPKPWGIZ-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000005828 Pyrimethanil Substances 0.000 title abstract 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims description 33
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000007530 organic bases Chemical class 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- -1 guanidines hydrochloride Chemical class 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 150000002357 guanidines Chemical class 0.000 abstract description 2
- 239000012452 mother liquor Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract 4
- FHOQBEFKSSAXDW-UHFFFAOYSA-N carbamimidoyl(phenyl)azanium;chloride Chemical compound [Cl-].NC([NH3+])=NC1=CC=CC=C1 FHOQBEFKSSAXDW-UHFFFAOYSA-N 0.000 abstract 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000008059 anilinopyrimidines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000123650 Botrytis cinerea Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of pesticide, and relates to a preparation technology of agricultural bactericide, in particular to a preparation technology of pyrimethanil. The technology takes aniline, cyanamide and acetylacetone as raw materials, and at least comprises guanidine salt preparation, acidity adjustment as well as cyclization and post-treatment processes; the technology is characterized by comprising the steps of: taking C2-C5 monohydric alcohol as solvent; preparing phenyl guanidine hydrochloride by catalysis of hydrogen chloride under the condition that the pH value is 3-4; leading the prepared phenyl guanidine hydrochloride to directly have reaction with the acetylacetone without separation under the condition that organic alkali exists to obtain the pyrimethanil. The technology realizes preparation by a 'one-pot' method, and has the advantages of being simple in operation, less in solvent consumption, short in reaction period, easy to control, good in product purity, high in yield, simple in post-treatment technology and the like. Meanwhile, the mother liquor filtered by the method can be recycled, so that the environmental pollution is not caused, and the method is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of pesticide, relate to the technology of preparing of disinfectant use in agriculture, particularly the technology of preparing of phonetic mould amine.
Background technology
Phonetic mould amine is a kind of efficient, wide spectrum, low toxicity sterilant.
Chemical name: N-(4,6-dimethyl pyrimidine-2-yl) aniline
Molecular formula: C
12H
13N
3
Relative molecular weight: 199
Structural formula:
Phonetic mould amine is a kind of new and effective, low toxicity anilino-pyrimidine series bactericidal agent, novel structure, and the mechanism of action is unique, through the generation of inhibition infection process enzyme, thereby stops infecting and kill pathogens of germ.Especially the botrytis cinerea that non-anilino-pyrimidine series bactericidal agent commonly used has been developed immunity to drugs is effective, inhales conduction and stifling germicidal action in disease is had, and is mainly used in the diseases such as gray mold of control tomato, cucumber and grape, and market potential is huge.
The method of traditional synthetic phonetic mould amine; With aniline is starting raw material; For example CN 1631882 patents are raw material with aniline, cyanamide, under the condition that catalyzer hydrogenchloride exists, make the guanidines supercarbonate with alkaline carbonate as neutralizing agent, react with methyl ethyl diketone without separating directly; But aftertreatment is loaded down with trivial details and need the consumption high amounts of solvents, and cost is higher.
It is raw material that US 0137033 patent discloses with aniline, cyanamide, and there is down synthetic phonetic mould amine in synthesis of phenyl guanidinesalt in the presence of hydrochloric acid without being separated in mineral alkali sodium hydroxide, and yield has only 81.3%.
Summary of the invention
The object of the present invention is to provide a kind of new synthetic process, it is complicated to solve phonetic mould amine traditional synthesis aftertreatment, and the problem that yield is low realizes " one pot reaction " of real meaning reducing manufacturing cost, improves content and yield.
The objective of the invention is to realize like this, adopt alcoholic solvent and organic bases system, adjustment is the polarity of the phonetic mould amine popular response system of body material with aniline, cyanamide and methyl ethyl diketone, and the assurance reaction is carried out by expection smoothly; Simultaneously; Utilize the solubility with temperature of phonetic mould amine in alcoholic solvent to change and the temperature-resistant characteristics of the dissolving power of rest part; Adopt the isolating mode of low temperature crystallization effectively to simplify aftertreatment technology, simultaneously, effectively guarantee the content and the high yield of product.
Reaction equation is following:
The preparation method of the phonetic mould amine that the present invention relates to; With aniline, cyanamide and methyl ethyl diketone is raw material, comprises guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, and it is characterized in that: the monohydroxy-alcohol with C2～C5 is a solvent; Under pH 3～4 conditions; Hydrogenchloride catalytic preparation guanidines hydrochloride, direct down and methyl ethyl diketone reaction obtains phonetic mould amine without the existence that is separated in organic bases.
The preparation method of the phonetic mould amine that the present invention relates to, aniline, cyanamide and methyl ethyl diketone are raw material, comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, it is characterized in that: said solvent is selected from a kind of in ethanol, Virahol, the trimethyl carbinol.
The preparation method of the phonetic mould amine that the present invention relates to; Aniline, cyanamide and methyl ethyl diketone are raw material; At least comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process, it is characterized in that: said organic bases is selected from a kind of in sodium methylate, sodium ethylate, triethylamine, diethylamine, the pyridine.
The preparation method of the phonetic mould amine that the present invention relates to, aniline, cyanamide and methyl ethyl diketone are raw material, comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, it is characterized in that: the mass concentration of said hydrochloric acid is between 30%～37%.
The preparation method of the phonetic mould amine that the present invention relates to, aniline, cyanamide and methyl ethyl diketone are raw material, comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, it is characterized in that: the mass concentration of said cyanamide is between 30%～75%.
The preparation method of the phonetic mould amine that the present invention relates to is a raw material with aniline, cyanamide and methyl ethyl diketone, comprises guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, and it is characterized in that: postprocessing working procedures is 0～5 ℃ of Crystallization Separation.
The preparation method of the phonetic mould amine that the present invention relates to; Aniline, cyanamide and methyl ethyl diketone are raw material; At least comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process, it is characterized in that: the mol ratio of aniline, cyanamide, methyl ethyl diketone is between 1:1～1.5:1～1.2.
The preparation method of the phonetic mould amine that the present invention relates to, aniline, cyanamide and methyl ethyl diketone are raw material, comprise guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, specific operation process is:
The guanidinesalt preparation: add aniline, alcohol under the room temperature, mix, dripping hydrochloric acid is warming up to 75～80 ℃ and drips cyanamide to pH 3～4, and reaction 3～6h obtains the guanidines hydrochloride, and the dripping hydrochloric acid hierarchy of control is kept pH 3～4;
Acidity adjustment and cyclisation: reaction system is reduced to room temperature, drips organic bases adjustment acidity and reaches 8～9 to pH, and the adding methyl ethyl diketone is warming up to 80～90 ℃ of reaction 4～6h, obtains phonetic mould amine aqueous solution;
Aftertreatment: be cooled to 0～5 ℃ of crystallization, filtering separation obtains the phonetic mould amine of title product.
The preparation method of the phonetic mould amine that the present invention relates to has realized " one kettle way " preparation, and reaction time is short, is easy to control, and product purity is good, yield is high, and aftertreatment technology is simple.
Preparing method's solvent system of the phonetic mould amine that the present invention relates to is reusable, effectively reduces cost, and the recyclable alcohol of the mother liquor after the filtration is reused.Do not produce environmental pollution, be particularly suitable for suitability for industrialized production.
Four, embodiment
Below in conjunction with embodiment the technical scheme that invention relates to is further specified, so that help understanding of the present invention, but not as the restriction to technical scheme.
Embodiment one
Room temperature adds 15g (98%; 0.158mol) aniline, 50ml ethanol; The back that stirs drips 37% hydrochloric acid regulation system pH value and reaches 3, be warming up to 70～80 ℃ of dropping 24.4g (30%, 0.174mol) cyanamide; Drip back flow reaction 3h, the mode hierarchy of control acidity with dripping hydrochloric acid in the process maintains between the pH 3～4; The alcohol sodium alcohol solution adjusting acidity of reducing to 20 ℃ of slow Dropwise 5s 0% reaches 9 to pH, and stirring 15min adds 17.7g (98%; 0.174mol) methyl ethyl diketone, the system that is warming up to refluxes under stirring, and keeps back flow reaction 4h; Be cooled to 0 ℃, 0～5 ℃ of crystallization, suction filtration obtains product 30.5g; Content 98.5%, yield 95.4%.
Embodiment two
Room temperature adds 15g (98%; 0.158mol) aniline, 50ml Virahol; The back that stirs drips 30% hydrochloric acid adjustment pH and reaches 4, be warming up to then 65～75 ℃ drip 20.1g (50%, 0.24mol) cyanamide; Drip 70～80 ℃ of reaction 4.5h, in the process with the mode maintenance system pH of dripping hydrochloric acid between 3～4; System is cooled to 25 ℃, slowly drips 30% methanol solution of sodium methylate and regulates acidity and reach 8 to pH, stirs 15min, adds 16.1g (98%; 0.158mol) methyl ethyl diketone, stirring down, system is warming up to backflow, back flow reaction 5h; Be cooled to 0 ℃, 0～5 ℃ of crystallization, suction filtration; Obtain product 30.7g, content 98.8%, yield 96.3%.
Embodiment three
Room temperature adds 15g (98%; 0.158mol) aniline, 50ml propyl carbinol; The hydrochloric acid adjustment pH of back Dropwise 35 % of stirring reaches 3～4, be warming up to then 80～90 ℃ drip 8.8g (75%, 0.158mol) cyanamide; Drip 80～90 ℃ of reaction 4h, in the reaction process with the mode hierarchy of control pH 3～4 of dripping hydrochloric acid; The pyridine adjusting acidity that system is cooled to 23 ℃ of slow droppings 99% reaches 8 to pH, and stirring 15min adds 19.3g (98%; 0.19mol) methyl ethyl diketone, stir 80～85 ℃ of reactions of system intensification 6h down, be cooled to 0 ℃; 0～5 ℃ of crystallization, suction filtration obtains product 31g; Content 97.7%, yield 96.1%.
Embodiment four
Room temperature adds 15g (98%; 0.158mol) aniline, 50ml propyl alcohol; The back that stirs drips 25% hydrochloric acid adjustment pH and reaches 3～4, be warming up to then 80～85 ℃ drip 12.5g (80%, 0.237mol) cyanamide; Drip 85～95 ℃ of reaction 6h, in the reaction process with the mode hierarchy of control pH 3～4 of dripping hydrochloric acid; The triethylamine adjusting acidity that system is cooled to 20 ℃ of slow droppings 99% reaches 8 to pH, and stirring 15min adds 20.4g (98%; 0.2mol) methyl ethyl diketone, stir 80～90 ℃ of reactions of system intensification 4h down, be cooled to 0 ℃; 0～5 ℃ is stirred the 30min crystallization, and suction filtration obtains product 31.3g; Content 98.2%, yield 97.6%.
Embodiment five
Room temperature adds 15g (98%; 0.158mol) aniline, the 50ml trimethyl carbinol; The back that stirs drips 37% hydrochloric acid adjustment pH and reaches 3～4, be warming up to then 75～85 ℃ drip 14.4g (60%, 0.21mol) cyanamide; Drip 75～85 ℃ of reaction 4h, in the reaction process with the mode hierarchy of control pH 3～4 of dripping hydrochloric acid; The diethylamine adjusting acidity that system is cooled to 20 ℃ of slow droppings 98% reaches 8 to pH, and stirring 15min adds 18.3g (98% again; 0.18mol) methyl ethyl diketone, stir refluxed reaction 3.5h, be cooled to 0 ℃; 0～5 ℃ is stirred the 30min crystallization, and suction filtration obtains product 30.8g; Content 97.8%, yield 95.6%.
Claims (8)
1. the preparation method of a phonetic mould amine; With aniline, cyanamide and methyl ethyl diketone is raw material, comprises guanidinesalt preparation, acidity adjustment and cyclisation and last handling process at least, and it is characterized in that: the monohydroxy-alcohol with C2～C5 is a solvent; Under pH 3～4 conditions; Hydrogenchloride catalytic preparation guanidines hydrochloride, direct down and methyl ethyl diketone reaction obtains phonetic mould amine without the existence that is separated in organic bases.
2. the preparation method of phonetic mould amine according to claim 1 is characterized in that: said solvent is selected from a kind of in ethanol, Virahol, the trimethyl carbinol.
3. the preparation method of phonetic mould amine according to claim 1 is characterized in that: said organic bases is selected from a kind of in sodium methylate, sodium ethylate, triethylamine, diethylamine, the pyridine.
4. the preparation method of phonetic mould amine according to claim 1, it is characterized in that: the mass concentration of said hydrochloric acid is between 30%～37%.
5. the preparation method of phonetic mould amine according to claim 1, it is characterized in that: the mass concentration of said cyanamide is between 30%～75%.
6. the preparation method of phonetic mould amine according to claim 1, it is characterized in that: postprocessing working procedures is 0～5 ℃ of Crystallization Separation.
7. the preparation method of phonetic mould amine according to claim 1, it is characterized in that: the mol ratio of aniline, cyanamide, methyl ethyl diketone is between 1:1～1.5:1～1.2.
8. according to the described preparation method of phonetic mould amine arbitrarily of claim 1～7, specific operation process is:
The guanidinesalt preparation: add aniline, alcohol under the room temperature, mix, dripping hydrochloric acid is warming up to 70～90 ℃ and drips cyanamide to pH 3～4, and reaction 3～6h obtains the guanidines hydrochloride, and the dripping hydrochloric acid hierarchy of control is kept pH 3～4;
Acidity adjustment and cyclisation: reaction system is reduced to room temperature, drips organic bases adjustment acidity and reaches 8～9 to pH, and the adding methyl ethyl diketone is warming up to 80～90 ℃ of reaction 4～6h, obtains phonetic mould amine aqueous solution;
Aftertreatment: be cooled to 0～5 ℃ of crystallization, filtering separation obtains the phonetic mould amine of title product.
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| CN201210301619.7A CN102816122B (en) | 2012-08-23 | 2012-08-23 | Preparation method of pyrimethanil |
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Cited By (7)
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| CN109020964A (en) * | 2018-08-28 | 2018-12-18 | 李金铃 | A kind of fungicide and its application |
| CN109020965A (en) * | 2018-08-28 | 2018-12-18 | 李金铃 | A kind of fungicide and its application |
| CN109053703A (en) * | 2018-08-28 | 2018-12-21 | 李金铃 | A kind of fungicide and its application |
| CN109053704A (en) * | 2018-08-28 | 2018-12-21 | 李金铃 | A kind of fungicide and its application |
| CN109134442A (en) * | 2018-08-28 | 2019-01-04 | 李金铃 | A kind of fungicide and its application |
| CN109232543A (en) * | 2018-08-28 | 2019-01-18 | 李金铃 | A kind of fungicide and its application |
| CN110330447A (en) * | 2019-07-16 | 2019-10-15 | 北京赛升药业股份有限公司 | A kind of preparation method and applications of Nafamostat Mesilate intermediate |
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| CN109020965A (en) * | 2018-08-28 | 2018-12-18 | 李金铃 | A kind of fungicide and its application |
| CN109053703A (en) * | 2018-08-28 | 2018-12-21 | 李金铃 | A kind of fungicide and its application |
| CN109053704A (en) * | 2018-08-28 | 2018-12-21 | 李金铃 | A kind of fungicide and its application |
| CN109134442A (en) * | 2018-08-28 | 2019-01-04 | 李金铃 | A kind of fungicide and its application |
| CN109232543A (en) * | 2018-08-28 | 2019-01-18 | 李金铃 | A kind of fungicide and its application |
| CN110330447A (en) * | 2019-07-16 | 2019-10-15 | 北京赛升药业股份有限公司 | A kind of preparation method and applications of Nafamostat Mesilate intermediate |
| CN110330447B (en) * | 2019-07-16 | 2022-04-15 | 北京赛升药业股份有限公司 | Preparation method and application of nafamostat mesylate intermediate |
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