CN102659623A - Method for synthesizing trifloxystrobin - Google Patents
Method for synthesizing trifloxystrobin Download PDFInfo
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- CN102659623A CN102659623A CN2012101465149A CN201210146514A CN102659623A CN 102659623 A CN102659623 A CN 102659623A CN 2012101465149 A CN2012101465149 A CN 2012101465149A CN 201210146514 A CN201210146514 A CN 201210146514A CN 102659623 A CN102659623 A CN 102659623A
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Abstract
The invention discloses a method for synthesizing trifloxystrobin. Liquid bromine, (E)-2-(2-methyl phenyl)-2-methoxyimno methyl acetate and sodium acetate which are taken as raw materials are subjected to catalytic reaction in a system of an organic solvent and water by taking fluorescent powder and a fluorescent lamp as light sources to form the product. The method comprises the following steps: completely dissolving the raw materials; preparing a trifloxystrobin intermediate through catalytic reaction; preparing an alkaline solution of trifluoromethylacetophenone oxime; and reacting the alkaline solution of trifluoromethylacetophenone oxime with the trifloxystrobin intermediate to obtain the target product trifloxystrobin. The invention has the advantages that the preparation method is simple, practical, high in efficiency, safe and convenient, the product is high in purity and yield, the yield of the final product is over 98 percent, and the purity of the final product is over 95 percent; during synthesis, adopted reagents are low in toxicity and high in economy and have a few side reactions; and because the solvent is recycled, the production cost and the danger coefficient are greatly reduced, the economy is high, and the trifloxystrobin is suitable for industrial large-scale production and meets the current increasing market demand.
Description
Technical field
The present invention relates to the preparation of fine chemical product, particularly a kind of compound method of oxime bacterium ester.
Background technology
Oxime bacterium ester: English name Trifloxystrobin; Chinese another name: oxime bacterium fat, (2Z)-2-methoxyimino-2-[2-[[1-[3-(trifluoromethyl) phenyl] ethyleneimino] oxygen methyl] phenyl] methyl acetate, quick, the careless ester of oxime of trifluoro; Chemical substance accession number (CAS number) is 141517-21-7, and molecular formula is C
20H
19F
3N
2O
4, molecular weight is 408.37, fusing point: 72.9 ℃, boiling point: 312 ℃, structural formula is following:
Oxime bacterium ester class wide-spectrum bactericide is one type of new fluorine-containing sterilant successfully developing as the sterilant lead compound with natural product methoxy acrylic (Strobilurins); Characteristics such as having efficient, wide spectrum, protection, treat, root out, infiltration, systemic activity, resistance of rainwater washing against, lasting period are long; To 1; The bacterial strain of 4-demethylation enzyme inhibitors, benzamides, dicarboxyl amine and benzimidazoles generation resistance is effective, does not have cross resistance with at present existing sterilant.It all has good activity to nearly all Eumycetes (Ascomycetes, Basidiomycetes, Oomycete and imperfect fungi) disease such as Powdery Mildew, rust, Ying's rot, net blotch, oidium, rice blast etc.; Except that Powdery Mildew, leaf spot are had the special efficacy; Rust, oidium, damping-off, apple apple scab there is good activity; Can be by plant wax layer strong adsorption; To plant surface excellent protection activity is provided, is mainly used in grape, apple, wheat, peanut, banana, vegetables etc. and carries out cauline leaf processing, control.Oxime bacterium ester is capable of being fast degraded in soil, in the water, so environmentally safe.Oxime bacterium ester mainly obtains through 2-halogenated methyl-α-methoxy imino methyl phenylacetate and the condensation of m-trifluoromethyl acetophenone oxime, wherein halogen chlorine or bromine normally.But the important intermediate of this type of relatively novel fluorine-containing sterilant at present, but high, the danger coefficient big (especially utilizing peroxo-reagent) of its production cost in bromination process has influenced the industrialized further production of oxime bacterium ester to a great extent.So (E)-success of 2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate is synthetic to have very high practical value for the promotion efficiency that reduces the industriallization danger coefficient, increases this sterilant; And production cost reduces; Can bring better economic benefit, help applying of synthesis technique.
(E)-and 2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate, structural formula is following:
At present to have be with peroxo-reagent catalytic bromination process to the main method of synthetic this compound, has numerous shortcomings: 1) reaction not exclusively, product purity is low, be difficult to industrialized method purifying, and the thick product instability that obtains of this method; 2) bromination process is difficult to control, is easy to generate dibromide; 3) because reaction is incomplete, and one ton of product of every production just produces 18 tons of brominated waste water, intractability is big, environmental pollution is serious; 4) unstable chemcial property is heated, rubs, clashes into and be prone to cause decomposition, burning, even blasts, and more unstable when dry, meeting sulfuric acid can burn, and purity requirement is high, and the impurity of trace promptly brings the difficulty that reduces productive rate and purity.Because above-mentioned existing problems particularly cause combustion explosion easily, the scope of use reduces year by year, and each big chemical industry is also early forbidden in the world.Relevant document with peroxo-reagent preparation (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate is referring to [1] Yang Yubin. chemical science and technology dynamic [M]. and Beijing: Chemical Industry Press; 1996:1-3, [2] Ishihara Mining & Chemical CO.A-(4-(5-Fluoromethyl-2-pyridyloxy) phenolxy) Alkanecarboxylic Acid Derivatives and Its Uses as a Herbicide:GB; 1599126 [P] .1981-09-30, [3] Wang Shuan; Zhang Rongjin; Ye Fei. the progress of acetyl-CoA carboxylase inhibitor [J]. pesticide science and management; 2003,24 (20): 26-32, [4] strong victory. weeds are learned [M]. Beijing: Chinese agriculture press, 2001:176-177.Also there is document under illumination condition, to prepare (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate with the liquid bromine; Total recovery is less than 60%; Satisfy not shortcomings such as reaction owing to receive restriction, the light source of purity and productive rate, also be not suitable for the scale operation of industry.Present oxime bacterium ester production company also attempts studying with various light sources, but does not all have practical value and fail because bromide reagent and raw material reaction efficient are too low.
For these reasons, be badly in need of a kind ofly having the economy height at present, yield is good, side reaction is few and environmental pollution is little, round-the-clock and safe ready strengthen the throughput of the sterilant of this kind excellent property by synthetic (the E)-2-(2-2-bromomethylphenyl) of (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate-2-methoxy imino methyl acetate raw material.We have carried out deep research test on the empirical basis in the past to this test, have finally found to meet the TP and the condition of above-mentioned requirements.
The report of contrast pertinent literature and patent; The present invention has following some advantage: 1) adopt commercially available high-efficiency fluorescence powder make reaction can with common fluorescent lamp illumination provide light source catalytic liquid bromine with (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate raw material highly effective reaction, safe ready has synthesized purity fast and has reached the midbody more than 95%; 2) adopting organic solvent and water etc. is solvent system, in document in the past, does not almost have this kind method; 3) solvent cycle that adopts is utilized cheapness and environmental protection; 4) aftertreatment technology is simple, can reach the productive rate more than 98%, and 18 tons of wastewater flow rates that original explained hereafter product per ton produces are reduced to 0, and this technology is process for cleanly preparing, so the present invention has very high meliority in industrial production.
Summary of the invention
The objective of the invention is to above-mentioned existing problems, a kind of efficient, economic, green, safety is provided and has met the compound method of the oxime bacterium ester that industrial production requires.
Technical scheme of the present invention:
A kind of compound method of oxime bacterium ester; With liquid bromine, (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate, sodium-acetate is raw material, and fluorescent lamp is a light source, and fluorescent material is assisted excitation light source; In the system of organic solvent and water, carry out catalyzed reaction and make, step is following:
1) (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of organic solvent and water, stir raw material is dissolved back adding sodium-acetate fully, at room temperature stirred then 30 minutes;
2) dropping liquid bromine in above-mentioned solution; The drop rate of liquid bromine be per 5 seconds 1, dropwise back reaction 20 minutes under the fluorescent lamp illumination condition, add fluorescent material then and assist excitation light source; And after continuing to react 30 minutes under the fluorescent lamp illumination condition, stop illumination; At room temperature continue stirring reaction 1 hour, and used saturated sodium bicarbonate aqueous solution and saturated aqueous common salt washing reaction liquid then respectively, use anhydrous MgSO
4After the drying, through filter, concentrate, precipitation obtains oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid after reclaiming solvent, reaction formula is following:
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used N; Dinethylformamide (DMF) dissolves the N that obtains (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate fully; Dinethylformamide (DMF) solution; Make the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under bathing sodium hydride is added N at nitrogen protection, cryosel; Behind the dinethylformamide (DMF); Fluorine trimethylacetophenone oxime between agitation condition following minute four times adds between each the adding 1/4th of fluorine trimethylacetophenone oxime total mass, obtains an alkaline solution of fluorine trimethylacetophenone oxime;
5) with above-mentioned steps 4) preparation between after the alkaline solution of fluorine trimethylacetophenone oxime is cooled to-5～0 ℃, splash into above-mentioned steps 3) N of the oxime bacterium ester midbody of preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again and continue to stir 2 hours, add volume then and stirred 1 hour, cross and filter oxime bacterium ester bullion for the tap water of 1.5 times of this reaction solution TVs; After petroleum ether, can make target product oxime bacterium ester.
Said organic solvent is tetracol phenixin, chloroform, methylene dichloride, 1,2-ethylene dichloride, acetonitrile, N, dinethylformamide (DMF) or dioxane; The volume ratio of organic solvent and water is 5: 1 in the mixed solution of organic solvent and water; Mixed solution with (E)-the quality amount ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate for will (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate whole dissolving excessive 15-25% also; Sodium-acetate with (E)-mass ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is 0.35-0.45: 1.
Said luminescent lamp is a T8 type low-pressure mercury vapour arc discharge lamp, and power is 65W-85W.
Luminescent lamp adopts T8 type low-pressure mercury vapour arc discharge lamp, and about 3% energy is converted into visible light in discharge, and its main wavelength is 405nm (royal purple light), 436nm (blue light), 456nm (green glow) and 577nm (gold-tinted).Uv-radiation shines on the fluorescent coating of tube inner wall, and ultraviolet energy is absorbed by fluorescent material, and wherein a part is converted into visible light and discharges.The visible light that sends in typical luminescent lamp is about as much as 28% of input lamp self-energy.The geometrical dimension that the optical property of luminescent lamp depends primarily on fluorescent tube is length, diameter, coating fluorescent material and ME.
Said liquid bromine with (E)-mass ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is 1: 0.8-1.8.
The fluorescent material of the auxiliary excitation light source of said conduct is naphthalene, anthracene, 9; 10-dimethylanthracene, phenanthrene, resorcinolphthalein, pyrimidine anthrone, coumarin derivatives (white dyes 236) or UVNUL MS-40 disulfonic acid derivatives, the emmission spectrum wavelength of fluorescent material is 270-800nm; The mass ratio of said (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate and fluorescent material is 1: 0.01-0.05.
The N of said dissolving sodium hydride, the quality of dinethylformamide (DMF) is 35-40 a times of sodium hydride total mass; Between fluorine trimethylacetophenone oxime and N, the mass ratio of dinethylformamide (DMF) is 1: 10-11.
The mass ratio of the alkaline solution of said fluorine trimethylacetophenone oxime and oxime bacterium ester midbody is 1.1-1.5: 1.
Advantage of the present invention is: the preparation method is simple and practical, efficient is high, safe ready, and product purity is high, yield is high, and the yield of final product is more than 98%, and purity is more than 95%; The reagent toxicity that adopts in synthetic is low, economy is high and side reaction is few; Because the solvent cycle utilization reduces production cost and danger coefficient greatly, good economy performance, but commercialization scale operation satisfy the current ever-increasing market requirement.
Embodiment
Embodiment 1:
A kind of compound method of oxime bacterium ester, step is following:
1) in the 1L four-hole bottle that backflow and mechanical stirring device are housed; 13.5g (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of 435ml tetracol phenixin and 87ml water; Stirring is dissolved the back fully with raw material and is added the 4.87g sodium-acetate, at room temperature stirs then 30 minutes;
2) in above-mentioned system, drip 15g liquid bromine; The drop rate of liquid bromine be per 5 seconds 1; Dropwise back reaction 20 minutes under 65W luminescent lamp illumination condition, add commercially available fluorescent material anthracene (emission wavelength is 410nm) then and proceed illumination and stop illumination after 30 minutes reacting selected fluorescent lamp, at room temperature continue stirring reaction after 1 hour; Use saturated sodium bicarbonate aqueous solution, saturated aqueous common salt washing reaction liquid respectively, anhydrous MgSO
4Drying is filtered, is concentrated, precipitation makes oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid, solvent recuperation;
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used 150ml N, dinethylformamide (DMF) dissolves fully, makes the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under nitrogen protection, cryosel are bathed, the 5g sodium hydride is added 189.7gN, behind the dinethylformamide (DMF), divide equally four times under the agitation condition and add fluorine trimethylacetophenone oxime between 19g, obtain an alkaline solution of fluorine trimethylacetophenone oxime;
5) alkaline solution of fluorine trimethylacetophenone oxime between step 4) preparation is cooled to-5～0 ℃ after, splash into the N of the oxime bacterium ester midbody of step 3) preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again, stirring reaction adds the 150ml tap water and stirred 1 hour after 2 hours, crosses and filters oxime bacterium ester bullion; After the 50ml petroleum ether, can make target product oxime bacterium ester.
The nuclear-magnetism parameter of target product oxime bacterium ester is following:
1HNMR (CDCl
3), δ 1.90 (S, 3H, CH
3), 3.17 (S, 3H, CH
3), 4.01 (S, 3H, CH
3), 4.79 (S, 2H, CH
2), 7.20 (m, 4H, Ar-H), 7.60 (d, 2H, Ar-H), 7.80 (S, 1H, Ar-H).
Detect to show: transformation efficiency is 90%, confirms that through nuclear-magnetism (hydrogen spectrum, carbon spectrum), infrared, gas chromatograph product purity is 92%--93%.
Embodiment 2:
A kind of compound method of oxime bacterium ester, step is following:
1) in the 1L four-hole bottle that backflow and mechanical stirring device are housed; 18.6g (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of 480ml tetracol phenixin and 98ml water; Stirring is dissolved the back fully with raw material and is added the 4.87g sodium-acetate, at room temperature stirs then 30 minutes;
2) in above-mentioned system, drip 15g liquid bromine; The drop rate of liquid bromine be per 5 seconds 1; Dropwise back reaction 20 minutes under 80W luminescent lamp illumination condition, add commercially available pyrimidine anthrone (emission wavelength is 468nm) then and proceed illumination and stop illumination after 30 minutes reacting selected fluorescent lamp, at room temperature continue stirring reaction after 1 hour; Use saturated sodium bicarbonate aqueous solution, saturated aqueous common salt washing reaction liquid respectively, anhydrous MgSO
4Drying is filtered, is concentrated, precipitation makes oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid, solvent recuperation;
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used 150ml N, dinethylformamide (DMF) dissolves fully, makes the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under nitrogen protection, cryosel are bathed, the 5g sodium hydride is added 189.7gN, behind the dinethylformamide (DMF), divide equally four times under the agitation condition and add fluorine trimethylacetophenone oxime between 19g, obtain an alkaline solution of fluorine trimethylacetophenone oxime;
5) alkaline solution of fluorine trimethylacetophenone oxime between step 4) preparation is cooled to-5～0 ℃ after, splash into the N of the oxime bacterium ester midbody of step 3) preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again, stirring reaction adds the 150ml tap water and stirred 1 hour after 2 hours, crosses and filters oxime bacterium ester bullion; After the 50ml petroleum ether, can make target product oxime bacterium ester.
The nuclear-magnetism parameter of target product oxime bacterium ester is following:
1HNMR (CDCl
3), δ 1.90 (S, 3H, CH
3), 3.17 (S, 3H, CH
3), 4.01 (S, 3H, CH
3), 4.79 (S, 2H, CH
2), 7.20 (m, 4H, Ar-H), 7.60 (d, 2H, Ar-H), 7.80 (S, 1H, Ar-H).
Detect to show: transformation efficiency is 98%, confirms that through nuclear-magnetism (hydrogen spectrum, carbon spectrum), infrared, gas chromatograph product purity is 96%.
Embodiment 3:
A kind of compound method of oxime bacterium ester, step is following:
1) in the 1L four-hole bottle that backflow and mechanical stirring device are housed; 25.5g (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of 510ml tetracol phenixin and 102ml water; Stirring is dissolved the back fully with raw material and is added the 4.87g sodium-acetate, at room temperature stirs then 30 minutes;
2) in above-mentioned system, drip 15g liquid bromine; The drop rate of liquid bromine be per 5 seconds 1; Dropwise back reaction 20 minutes under 85W luminescent lamp illumination condition, add commercially available phenanthrene (emission wavelength is 330nm) then and proceed illumination and stop illumination after 30 minutes reacting selected fluorescent lamp, at room temperature continue stirring reaction after 1 hour; Use saturated sodium bicarbonate aqueous solution, saturated aqueous common salt washing reaction liquid respectively, anhydrous MgSO
4Drying is filtered, is concentrated, precipitation makes oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid, solvent recuperation;
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used 150ml N, dinethylformamide (DMF) dissolves fully, makes the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under nitrogen protection, cryosel are bathed, the 5g sodium hydride is added 189.7gN, behind the dinethylformamide (DMF), divide equally under the agitation condition and add fluorine trimethylacetophenone oxime stirring between 19g for four times, obtain an alkaline solution of fluorine trimethylacetophenone oxime;
5) alkaline solution of fluorine trimethylacetophenone oxime between step 4) preparation is cooled to-5～0 ℃ after, splash into the N of the oxime bacterium ester midbody of step 3) preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again, stirring reaction adds the 150ml tap water and stirred 1 hour after 2 hours, crosses and filters oxime bacterium ester bullion; After the 50ml petroleum ether, can make target product oxime bacterium ester.
The nuclear-magnetism parameter of target product oxime bacterium ester is following:
1HNMR (CDCl
3), δ 1.90 (S, 3H, CH
3), 3.17 (S, 3H, CH
3), 4.01 (S, 3H, CH
3), 4.79 (S, 2H, CH
2), 7.20 (m, 4H, Ar-H), 7.60 (d, 2H, Ar-H), 7.80 (S, 1H, Ar-H).
Detect to show: transformation efficiency is 92%, confirms that through nuclear-magnetism (hydrogen spectrum, carbon spectrum), infrared, gas chromatograph product purity is 88%.
Embodiment 4:
A kind of compound method of oxime bacterium ester, step is following:
1) in the 1L four-hole bottle that backflow and mechanical stirring device are housed; 13.5g (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of 435ml tetracol phenixin and 87ml water; Stirring is dissolved the back fully with raw material and is added the 4.87g sodium-acetate, at room temperature stirs then 30 minutes;
2) in above-mentioned system, drip 15g liquid bromine; The drop rate of liquid bromine be per 5 seconds 1; Dropwise back reaction 20 minutes under 65W luminescent lamp illumination condition, add commercially available resorcinolphthalein (emission wavelength is 428nm) then and proceed illumination and stop illumination after 30 minutes reacting selected fluorescent lamp, at room temperature continue stirring reaction after 1 hour; Use saturated sodium bicarbonate aqueous solution, saturated aqueous common salt washing reaction liquid respectively, anhydrous MgSO
4Drying is filtered, is concentrated, precipitation makes oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid, solvent recuperation;
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used 150ml N, dinethylformamide (DMF) dissolves fully, makes the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under nitrogen protection, cryosel are bathed, the 5g sodium hydride is added 189.7gN, behind the dinethylformamide (DMF), divide equally under the agitation condition and add fluorine trimethylacetophenone oxime stirring between 19g for four times, obtain an alkaline solution of fluorine trimethylacetophenone oxime;
5) alkaline solution of fluorine trimethylacetophenone oxime between step 4) preparation is cooled to-5～0 ℃ after, splash into the N of the oxime bacterium ester midbody of step 3) preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again, stirring reaction adds the 150ml tap water and stirred 1 hour after 2 hours, crosses and filters oxime bacterium ester bullion; After the 50ml petroleum ether, can make target product oxime bacterium ester.
The nuclear-magnetism parameter of target product oxime bacterium ester is following:
1HNMR (CDCl
3), δ 1.90 (S, 3H, CH
3), 3.17 (S, 3H, CH
3), 4.01 (S, 3H, CH
3), 4.79 (S, 2H, CH
2), 7.20 (m, 4H, Ar-H), 7.60 (d, 2H, Ar-H), 7.80 (S, 1H, Ar-H).
Detect to show: transformation efficiency is 93%, confirms that through nuclear-magnetism (hydrogen spectrum, carbon spectrum), infrared, gas chromatograph product purity is 92%.
Claims (7)
1. the compound method of an oxime bacterium ester; It is characterized in that: with liquid bromine, (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate, sodium-acetate is raw material, and fluorescent lamp is a light source, and fluorescent material is assisted excitation light source; In the system of organic solvent and water, carry out catalyzed reaction and make, step is following:
1) (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is added in the mixed solution of organic solvent and water, stir raw material is dissolved back adding sodium-acetate fully, at room temperature stirred then 30 minutes;
2) dropping liquid bromine in above-mentioned solution; The drop rate of liquid bromine be per 5 seconds 1, dropwise back reaction 20 minutes under the fluorescent lamp illumination condition, add fluorescent material then and assist excitation light source; And after continuing to react 30 minutes under the fluorescent lamp illumination condition, stop illumination; At room temperature continue stirring reaction 1 hour, and used saturated sodium bicarbonate aqueous solution and saturated aqueous common salt washing reaction liquid then respectively, use anhydrous MgSO
4After the drying, through filter, concentrate, precipitation obtains oxime bacterium ester midbody (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid after reclaiming solvent;
3) above-mentioned (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate solid is used N; Dinethylformamide (DMF) dissolves the N that obtains (E)-2-(2-2-bromomethylphenyl)-2-methoxy imino methyl acetate fully; Dinethylformamide (DMF) solution; Make the N of oxime bacterium ester midbody, dinethylformamide (DMF) solution;
4) under bathing sodium hydride is added N at nitrogen protection, cryosel; Behind the dinethylformamide (DMF); Fluorine trimethylacetophenone oxime between agitation condition following minute four times adds between each the adding 1/4th of fluorine trimethylacetophenone oxime total mass, obtains an alkaline solution of fluorine trimethylacetophenone oxime;
5) with above-mentioned steps 4) preparation between after the alkaline solution of fluorine trimethylacetophenone oxime is cooled to-5～0 ℃, splash into above-mentioned steps 3) N of the oxime bacterium ester midbody of preparation, in dinethylformamide (DMF) solution; Dropwise back stirring reaction 1 hour in-5～0 ℃ of scope; Rise to room temperature again and continue to stir 2 hours, add volume then and stirred 1 hour, cross and filter oxime bacterium ester bullion for the tap water of 1.5 times of this reaction solution TVs; After petroleum ether, can make target product oxime bacterium ester.
2. according to the compound method of the said oxime bacterium of claim 1 ester, it is characterized in that: said organic solvent is tetracol phenixin, chloroform, methylene dichloride, 1,2-ethylene dichloride, acetonitrile, N, dinethylformamide (DMF) or dioxane; The volume ratio of organic solvent and water is 5: 1 in the mixed solution of organic solvent and water; Mixed solution with (E)-the quality amount ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate for will (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate whole dissolving excessive 15-25% also; Sodium-acetate with (E)-mass ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is 0.35-0.45: 1.
3. according to the compound method of the said oxime bacterium of claim 1 ester, it is characterized in that: said luminescent lamp is a T8 type low-pressure mercury vapour arc discharge lamp, and power is 65W-85W.
4. according to the compound method of the said oxime bacterium of claim 1 ester, it is characterized in that: said liquid bromine with (E)-mass ratio of 2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate is 1: 0.8-1.8.
5. according to the compound method of the said oxime bacterium of claim 1 ester; It is characterized in that: the fluorescent material of the auxiliary excitation light source of said conduct is naphthalene, anthracene, 9; 10-dimethylanthracene, phenanthrene, resorcinolphthalein, pyrimidine anthrone, coumarin derivatives (white dyes 236) or UVNUL MS-40 disulfonic acid derivatives, the emmission spectrum wavelength of fluorescent material is 270-800nm; The mass ratio of said (E)-2-(2-aminomethyl phenyl)-2-methoxy imino methyl acetate and fluorescent material is 1: 0.01-0.05.
6. according to the compound method of the said oxime bacterium of claim 1 ester, it is characterized in that: the N of said dissolving sodium hydride, the quality of dinethylformamide (DMF) is 35-40 a times of sodium hydride total mass; Between fluorine trimethylacetophenone oxime and N, the mass ratio of dinethylformamide (DMF) is 1: 10-11.
7. according to the compound method of the said oxime bacterium of claim 1 ester, it is characterized in that: the mass ratio of the alkaline solution of said fluorine trimethylacetophenone oxime and oxime bacterium ester midbody is 1.1-1.5: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952036A (en) * | 2012-11-18 | 2013-03-06 | 大连九信生物化工科技有限公司 | Preparation method of trifloxystrobin |
| CN103787916A (en) * | 2014-01-15 | 2014-05-14 | 京博农化科技股份有限公司 | Preparation method of trifloxystrobin |
| CN113912513A (en) * | 2021-11-19 | 2022-01-11 | 青岛恒宁生物科技有限公司 | Preparation method of oximido acetate compound and intermediate thereof |
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2012
- 2012-05-11 CN CN2012101465149A patent/CN102659623A/en active Pending
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| CN102952036A (en) * | 2012-11-18 | 2013-03-06 | 大连九信生物化工科技有限公司 | Preparation method of trifloxystrobin |
| CN103787916A (en) * | 2014-01-15 | 2014-05-14 | 京博农化科技股份有限公司 | Preparation method of trifloxystrobin |
| CN103787916B (en) * | 2014-01-15 | 2016-07-13 | 京博农化科技股份有限公司 | A kind of preparation method of trifloxystrobin |
| CN113912513A (en) * | 2021-11-19 | 2022-01-11 | 青岛恒宁生物科技有限公司 | Preparation method of oximido acetate compound and intermediate thereof |
| CN113912513B (en) * | 2021-11-19 | 2024-01-26 | 青岛恒宁生物科技有限公司 | Preparation method of oximido acetate compound and intermediate thereof |
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Application publication date: 20120912 |