CN103524379A - Synthesis method of trifloxystrobin - Google Patents
Synthesis method of trifloxystrobin Download PDFInfo
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- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 title abstract description 3
- 238000001308 synthesis method Methods 0.000 title abstract 4
- 239000005857 Trifloxystrobin Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 32
- 241000894006 Bacteria Species 0.000 claims description 27
- 150000002148 esters Chemical class 0.000 claims description 27
- 150000002923 oximes Chemical class 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010189 synthetic method Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 238000007086 side reaction Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 206010011409 Cross infection Diseases 0.000 abstract 1
- 206010029803 Nosocomial infection Diseases 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 238000005070 sampling Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZKHQWZAMYRWXGA-KQYNXXCUSA-N Adenosine triphosphate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-N 0.000 description 2
- 241000221785 Erysiphales Species 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003612 virological effect Effects 0.000 description 2
- 241000235349 Ascomycota Species 0.000 description 1
- 241000221198 Basidiomycota Species 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000233654 Oomycetes Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000918585 Pythium aphanidermatum Species 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 229930182692 Strobilurin Natural products 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 229940054066 benzamide antipsychotics Drugs 0.000 description 1
- 150000003936 benzamides Chemical class 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002438 mitochondrial effect Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035806 respiratory chain Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of trifloxystrobin. A reaction process of the synthesis method includes water diversion treatment. By virtue of a water carrying process, the influence of water formed in the reaction on the reaction is effectively avoided, thereby reducing side reaction, and improving product yield and product quality. According to the synthesis method, a reaction liquid solvent is directly used for crystallization after the reaction so as to avoid change of a crystallization solvent and to avoid cross infection of the solvents, thus further enhancing product quality.
Description
Technical field
The present invention relates to a kind of synthetic method of oxime bacterium ester.
Background technology
Oxime bacterium ester (Trifloxystrobin) class wide-spectrum bactericide is the new fungicides of a class of successfully developing as sterilant lead compound from natural product Strobilurins.Characteristics such as thering is efficient, wide spectrum, protection, treat, root out, infiltration, interior suction, activity, resistance of rainwater washing against, lasting period are long.To 1,4-demethylation enzyme inhibitors, benzamides, the bacterial strain of dicarboxyl amine and benzimidazoles generation resistance is effective, without cross resistance, nearly all Eumycetes (Ascomycetes, Basidiomycetes, Oomycete and imperfect fungi) disease is all had to good activity as Powdery Mildew, rust, glume blight, net blotch, white viral disease, rice blast etc. with current existing sterilant.Go out Powdery Mildew, leaf spot are had outside special efficacy, rust, white viral disease, damping-off, apple apple scab are had to good activity.It is a kind of respiratory chain inhibitor, by the electronics transmission of pinning between cytochrome B and C1, stops cell Triphosaden (ATP) enzymic synthesis, thereby suppresses its mitochondrial respiratory and bring into play bacteriostatic action.To crop safety, because it is at soil, in water, can explain fast, therefore environmentally safe.On the synthetic document of oxime bacterium ester, report is a lot, and route is basic identical, but alkali used is different with solvent, but so far, still has many problems in preparation technology, and raw material seldom arrives, and technique is imperfect, and yield is low etc., to suitability for industrialized production, brings great difficulty.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and the synthetic method of a kind of economical and effective, the simple oxime bacterium of technique ester is provided.
For solving above technical problem, the present invention adopts following technical scheme:
A synthetic method for oxime bacterium ester, described synthetic method comprises the following steps:
A, to the agitator that is equipped with after nitrogen replacement, thermometer, in the reaction flask of water trap and condenser, add compound (I), alkaline matter and organic solvent also stir, be heated to reflux water-dividing, the described reflux water-dividing time is 5～6 hours, after dividing water to finish, be cooled to room temperature, then the toluene solution of compound (II) is added drop-wise in above-mentioned reaction solution, after dropwising, at room temperature be incubated 2～4 hours, wherein, described compound (I) is 1:1.0～3.0 with the mol ratio of alkaline matter, described compound (I) is 1:0.9～2.0 with the mol ratio of compound (II), the mass concentration of the toluene solution of described compound (II) is 30%～70%,
B, the reacted reacting liquid filtering of step a is obtained to mother liquor, in described mother liquor, add water, the part by weight of described mother liquor and water is 1:0.5～2.0, then stir, standing, layering, gained organic phase obtains oxime bacterium ester solution through washing, wherein, described washing be take the pH that washs rear water and was finished as 5～8 o'clock;
C, the oxime bacterium ester solution crystallisation by cooling that step b is obtained, filter and obtain white solid oxime bacterium ester.
Further, in step a, described alkaline matter is one or more the combination in sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.Described alkaline matter avoids using sodium methylate, sodium hydrogen, sodium amide, and adopts sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood, and cost of material is cheap, and security is good.
Further, in step a, described organic solvent is selected from benzene, toluene, hexanaphthene or dimethylbenzene.Described organic solvent avoids using N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), acetone, acetonitrile, and use the easily recovered solvent such as benzene, toluene, hexanaphthene or dimethylbenzene, can reduce costs, reduce environmental pollution.
Further, in step a, described in reaction process, minute water is the method that azeotropic divides water.
Further, in step c, the described cooling interim cooling method of taking.Described interim cooling is specific as follows: first oxime bacterium ester solution is cooled to 18 ℃～25 ℃, is incubated 0.5～1.5 hour, and then be cooled to 8 ℃～15 ℃, be incubated 1.5～2.5 hours, be finally cooled to 3 ℃～7 ℃, be incubated 3.5～4.5 hours.
In the present invention, all described raw material all can, by being purchased and/or taking known means to prepare, while not specified, all meet the requirement of stdn chemical product.
Due to the enforcement of technique scheme, the present invention compared with prior art tool has the following advantages:
In synthetic method of the present invention, there is turnout science and engineering skill, in reaction process, by band water process, effectively avoid the water forming in reaction on the impact of reacting, reduce the generation of side reaction, improve product yield and quality product.
Synthetic method of the present invention is after reaction finishes, and reacting liquid filtering obtains mother liquor, in mother liquor, adds water, then stirs, standing, layering, and gained organic phase washes with water and obtains oxime bacterium ester solution, and oxime bacterium ester solution crystallisation by cooling filters and obtains white solid oxime bacterium ester.In last process not to the solvent that adds other in reaction solution as recrystallisation solvent, but directly use the solvent of reaction solution as recrystallisation solvent, avoided changing the crossed contamination on the solvent that recrystallisation solvent causes.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), sodium hydroxide (4.2g, 0.100mol, 95%) and toluene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 6, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (35.6g, 95%), yield 82.9%.
Embodiment 2
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), potassium hydroxide (6.2g, 0.100mol, 90%) and benzene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 6.5, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (36.9g, 95%), yield 85.9%.
Embodiment 3
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), sodium hydroxide (4.2g, 0.100mol, 95%) and hexanaphthene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in hexanaphthene (20.0g), the cyclohexane solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7.5, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (37.1g, 95%), yield 86.4%.
Embodiment 4
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), potassium hydroxide (6.2g, 0.100mol, 90%) and hexanaphthene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in hexanaphthene (20.0g), the cyclohexane solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (38.0g, 95%), yield 88.5%.
Embodiment 5
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), salt of wormwood (14.5g, 0.100mol, 95%) and dimethylbenzene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (38.6g, 95%), yield 89.9%.
Embodiment 6
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), sodium carbonate (11.2g, 0.100mol, 95%) and dimethylbenzene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (37.6g, 95%), yield 87.5%.
Embodiment 7
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), sodium carbonate (22.3g, 0.200mol, 95%) and toluene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (58.7g, 0.195mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (35.3g, 95%), yield 82.1%.
Embodiment 8
To the agitator that is equipped with after nitrogen replacement, water trap, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), sodium carbonate (16.7g, 0.150mol, 95%) and toluene (45.0g), start to stir, be heated to reflux water-dividing, reflux 4 hours, divide water to finish, stop heating, be cooled to room temperature, by compound ii (45.1g, 0.15mol, 95%) be dissolved in toluene (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip 0.5 hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (36.5g, 95%), yield 84.9%.
Comparative example 1
To the agitator that is equipped with after nitrogen replacement, in the reaction flask of condenser and thermometer, add chemical compounds I (21.0g, 0.100mol, 97%), salt of wormwood (14.5g, 0.100mol, 95%) and N, dinethylformamide (45.0g), start to stir, control temperature of reaction at 50 ℃, be incubated 4 hours, be cooled to room temperature, by compound ii (31.6g, 0.105mol, 95%) be dissolved in N, dinethylformamide (20.0g), the toluene solution of compound ii is dropped in above-mentioned reaction solution, drip half an hour, 30 ℃ of insulations, be incubated after 3 hours, sampling analysis, after reaction finishes, processing reaction.In reaction solution, add water (50g) and hexanaphthene (50g), stir 10 minutes, standing, layering, organic phase washing (washing twice, each 50ml), after washing, the pH of water is 7, organic phase decrease temperature crystalline, and 20 ℃ are incubated 1 hour, part solid is separated out, 10 ℃ are incubated 2 hours, and 5 ℃ are incubated 4 hours, filter, obtain white solid oxime bacterium ester (32.3g, 95%), yield 75.2%.
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; and the invention is not restricted to the embodiments described; the equivalence that all spirit according to the present invention are done changes or modifies, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. a synthetic method for oxime bacterium ester, is characterized in that, described synthetic method comprises the following steps:
A, to the agitator that is equipped with after nitrogen replacement, thermometer, in the reaction flask of water trap and condenser, add compound (I), alkaline matter and organic solvent also stir, be heated to reflux water-dividing, the described reflux water-dividing time is 5～6 hours, after dividing water to finish, be cooled to room temperature, then the toluene solution of compound (II) is added drop-wise in above-mentioned reaction solution, after dropwising, at room temperature be incubated 2～4 hours, wherein, described compound (I) is 1:1.0～3.0 with the mol ratio of alkaline matter, described compound (I) is 1:0.9～2.0 with the mol ratio of compound (II), the mass concentration of the toluene solution of described compound (II) is 30%～70%,
B, the reacted reacting liquid filtering of step a is obtained to mother liquor, in described mother liquor, add water, the part by weight of described mother liquor and water is 1:0.5～2.0, then stir, standing, layering, gained organic phase obtains oxime bacterium ester solution through washing, wherein, described washing be take the pH that washs rear water and was finished as 5～8 o'clock;
C, the oxime bacterium ester solution crystallisation by cooling that step b is obtained, filter and obtain white solid oxime bacterium ester.
2. synthetic method according to claim 1, is characterized in that, in step a, described alkaline matter is one or more the combination in sodium hydroxide, potassium hydroxide, sodium carbonate and salt of wormwood.
3. synthetic method according to claim 1, is characterized in that, in step a, described organic solvent is selected from benzene, toluene, hexanaphthene or dimethylbenzene.
4. synthetic method according to claim 1, is characterized in that, in step a, described in reaction process, minute water is the method that azeotropic divides water.
5. synthetic method according to claim 1, is characterized in that, in step c, and the described cooling interim cooling method of taking.
6. synthetic method according to claim 5, it is characterized in that, in step c, described interim cooling is specific as follows: first oxime bacterium ester solution is cooled to 18 ℃～25 ℃, be incubated 0.5～1.5 hour, and then be cooled to 8 ℃～15 ℃, be incubated 1.5～2.5 hours, finally be cooled to 3 ℃～7 ℃, be incubated 3.5～4.5 hours.
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| CN117049981A (en) * | 2023-07-31 | 2023-11-14 | 沈阳感光化工研究院有限公司 | Preparation method of trifloxystrobin agricultural bactericide |
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| CN1321144A (en) * | 1998-09-30 | 2001-11-07 | 巴斯福股份公司 | Process for preparing trione bis (oxime ether) derivatives, and trione mono-and trione bis (oxime ether) derivatives obtained thereby |
| CN101941921A (en) * | 2010-09-03 | 2011-01-12 | 岳阳迪普化工技术有限公司 | Method for preparing trifloxystrobin |
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| CN1321144A (en) * | 1998-09-30 | 2001-11-07 | 巴斯福股份公司 | Process for preparing trione bis (oxime ether) derivatives, and trione mono-and trione bis (oxime ether) derivatives obtained thereby |
| CN101941921A (en) * | 2010-09-03 | 2011-01-12 | 岳阳迪普化工技术有限公司 | Method for preparing trifloxystrobin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117049981A (en) * | 2023-07-31 | 2023-11-14 | 沈阳感光化工研究院有限公司 | Preparation method of trifloxystrobin agricultural bactericide |
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