CN105218461A - A kind of method preparing Azoxystrobin - Google Patents
A kind of method preparing Azoxystrobin Download PDFInfo
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- CN105218461A CN105218461A CN201410281550.5A CN201410281550A CN105218461A CN 105218461 A CN105218461 A CN 105218461A CN 201410281550 A CN201410281550 A CN 201410281550A CN 105218461 A CN105218461 A CN 105218461A
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Abstract
The invention discloses a kind of method preparing Azoxystrobin, described method comprises the step generating Azoxystrobin: carry out formylation reaction in the presence of a catalyst by cumarone-2 (3H)-one and manthanoate, generate 3-formyl benzofuran-2 (3H)-one, the latter and methyl-sulfate carry out first oxidizing reaction and generate 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, again with 4, 6-dichloro pyrimidine and 2-cyanophenol react, generate Azoxystrobin, wherein: the mol ratio of reaction mass is: cumarone-2 (3H)-one: catalyzer: manthanoate: methyl-sulfate=1.0: 1.0 ~ 2.5: 1.0 ~ 10.0: 0.9 ~ 2.5, formylation reaction temperature-10 ~ 45 DEG C, 2 ~ 24 hours reaction times, first oxidizing reaction temperature 0 ~ 60 DEG C, 1 ~ 4 hour reaction times.The present invention has the advantages that technics comparing is simple, yield is high, cost compare is low.
Description
Technical field:
The present invention relates to technical field of chemistry and chemical engineering, more specifically to a kind of method preparing Azoxystrobin.
Background technology:
Azoxystrobin is methoxy acrylate (β-methoxyacrylates) sterilant or strobilurins analogue, there is the features such as efficient, wide spectrum, systemic activity are strong, good activity is all had to nearly all Eumycetes germ evil, can be used for cereal, paddy rice, grape, potato, vegetables, fruit tree and other stem of plant foliar spray mist, seed treatment, also can carry out soil treatment.Azoxystrobin uses to crop safety, without poisoning under recommended dose, to underground water and environmental safety.
The synthetic route of Azoxystrobin, all by 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, with 4, 6-dichloro pyrimidine and the reaction of 2-cyanophenol generate, wherein, 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one is reacted under diacetyl oxide exists by cumarone-2 (3H)-one and trimethyl orthoformate, namely diacetyl oxide makees the catalyzer reacted, generate methyl acetate with the methyl alcohol of by-product again simultaneously, reaction is proceeded, otherwise, reaction times is very long, reaction yield is very low, cost is high, and the methyl acetate that by-product is a large amount of.
Summary of the invention:
Object of the present invention is just to provide a kind of method preparing Azoxystrobin, technics comparing is simple, yield is high, cost compare is low feature that it has.
For achieving the above object, a kind of method preparing Azoxystrobin of the present invention, described method comprises the step generating Azoxystrobin: carry out formylation reaction in the presence of a catalyst by cumarone-2 (3H)-one and manthanoate, generate 3-formyl benzofuran-2 (3H)-one, the latter and methyl-sulfate carry out first oxidizing reaction and generate 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, again with 4, 6-dichloro pyrimidine and 2-cyanophenol react, generate Azoxystrobin, wherein: the mol ratio of reaction mass is: cumarone-2 (3H)-one: catalyzer: manthanoate: methyl-sulfate=1.0: 1.0 ~ 2.5: 1.0 ~ 10.0: 0.9 ~ 2.5, formylation reaction temperature-10 ~ 45 DEG C, 2 ~ 24 hours reaction times, first oxidizing reaction temperature 0 ~ 60 DEG C, 1 ~ 4 hour reaction times.
Preferred as technique scheme, described manthanoate is methyl-formiate or ethyl formate.
Preferred as technique scheme, described catalyzer is sodium salt or the sylvite of sodium hydride or alcohol.
Preferred as technique scheme, the sodium salt of described alcohol or sylvite are sodium methylate/potassium methylate, sodium ethylate/potassium ethylate, sodium propylate/potassium propylate, sodium isopropylate/potassium isopropoxide, sodium butylate/butanols potassium or sodium tert-butoxide/potassium tert.-butoxide.
Beneficial effect of the present invention is: the present invention has the advantages that technics comparing is simple, yield is high, cost compare is low.
Embodiment:
The following stated is only the preferred embodiment embodying the principle of the invention, does not therefore limit protection scope of the present invention
Embodiment 1:
In 500ml reaction flask, add dry DMF 200ml, methyl-formiate 30.0g, cumarone-2 (3H)-one 27g, stirring cools to less than-10 DEG C, drip the suspension liquid of sodium hydride in 200ml dry DMF of 12g60%, after dropping terminates, 0 DEG C, mixture reaction 2 hours, then add in 500g trash ice and be hydrolyzed, 200ml ether divides 2 washing hydrolyzed solutions, use 15% hydrochloric acid neutralizing hydrolysis liquid to pH4, 500ml ether divides 2 extraction hydrolyzed solutions, extracting solution is through anhydrous magnesium sulfate drying, reclaim ether and obtain pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-one.
Above-mentioned oily matter is dissolved in 150mlDMF, adds salt of wormwood 42g powder simultaneously, drips 32g methyl-sulfate under room temperature, after dropping terminates, continue insulation reaction 2 hours, add in 200ml water, 300ml ether divides three extraction hydrolyzed solutions, and suitable quantity of water washing ether extracted liquid, reclaims ether, add 30ml methyl alcohol, cooling crystallization, filters, obtains 32g pale yellow crystals 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, fusing point 100 ~ 101 DEG C, yield 90%.
Embodiment 2:
In 500ml reaction flask, add dry DMF 200ml, methyl-formiate 30.0g, cumarone-2 (3H)-one 27g, stirring cools to less than 0 DEG C, drip the suspension liquid of solid sodium methylate in 200ml dry DMF of 23g94%, after dropping terminates, mixture room temperature reaction 2 hours, then add in 500g trash ice and be hydrolyzed, 200ml ether divides 2 washing hydrolyzed solutions, use 15% hydrochloric acid neutralizing hydrolysis liquid to pH4, 500ml ether divides 2 extraction hydrolyzed solutions, extracting solution is through anhydrous magnesium sulfate drying, reclaim ether and obtain pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-one.
Above-mentioned oily matter is dissolved in 150mlDMF, adds salt of wormwood 42g powder simultaneously, drips 32g methyl-sulfate under room temperature, after dropping terminates, continue insulation reaction 2 hours, add in 200ml water, 300ml ether divides three extraction hydrolyzed solutions, and suitable quantity of water washing ether extracted liquid, reclaims ether, add 30ml methyl alcohol, cooling crystallization, filters, obtains 29g pale yellow crystals 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, fusing point 100 ~ 101 DEG C, yield 82%.
Embodiment 3:
In 500ml reaction flask, add dry DMF 200ml, methyl-formiate 30.0g, cumarone-2 (3H)-one 27g, stirring cools to less than-10 DEG C, drip the suspension liquid of potassium tert.-butoxide in 200ml dry DMF of 29g97%, after dropping terminates, 0 DEG C, mixture reaction 4 hours, then add in 500g trash ice and be hydrolyzed, 200ml ether divides 2 washing hydrolyzed solutions, use 15% hydrochloric acid neutralizing hydrolysis liquid to pH4, 500ml ether divides 2 extraction hydrolyzed solutions, extracting solution is through anhydrous magnesium sulfate drying, reclaim ether and obtain pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-one.
Above-mentioned oily matter is dissolved in 150mlDMF, adds salt of wormwood 35g powder simultaneously, drips 26g methyl-sulfate under room temperature, after dropping terminates, continue insulation reaction 2 hours, add in 200ml water, 300ml ether divides three extraction hydrolyzed solutions, and suitable quantity of water washing ether extracted liquid, reclaims ether, add 30ml methyl alcohol, cooling crystallization, filters, obtains 30g pale yellow crystals 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, fusing point 100 ~ 101 DEG C, yield 85%.
Embodiment 4:
In 500ml reaction flask, add dry DMF 200ml, ethyl formate 74.0g, cumarone-2 (3H)-one 27g, stirring cools to less than-10 DEG C, drip the suspension liquid of sodium ethylate in 200ml dry DMF of 29g96%, after dropping terminates, 0 DEG C, mixture reaction 8 hours, then add in 500g trash ice and be hydrolyzed, 200ml ether divides 2 washing hydrolyzed solutions, use 15% hydrochloric acid neutralizing hydrolysis liquid to pH4, 500ml ether divides 2 extraction hydrolyzed solutions, extracting solution is through anhydrous magnesium sulfate drying, reclaim ether and obtain pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-one.
Above-mentioned oily matter is dissolved in 150mlDMF, adds salt of wormwood 35g powder simultaneously, drips 26g methyl-sulfate under room temperature, after dropping terminates, continue insulation reaction 4 hours, add in 200ml water, 300ml ether divides three extraction hydrolyzed solutions, and suitable quantity of water washing ether extracted liquid, reclaims ether, add 30ml methyl alcohol, cooling crystallization, filters, obtains 30.5g pale yellow crystals 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, fusing point 100 ~ 101 DEG C, yield 86.5%.
Embodiment 5:
In 500ml reaction flask, add dry DMF 200ml, methyl-formiate 36.0g, cumarone-2 (3H)-one 27g, stirring cools to less than 0 DEG C, drip the suspension liquid of sodium isopropylate in 200ml dry DMF of 42g99%, after dropping terminates, 25 DEG C, mixture reaction 24 hours, then add in 500g trash ice and be hydrolyzed, 200ml ether divides 2 washing hydrolyzed solutions, use 15% hydrochloric acid neutralizing hydrolysis liquid to pH4, 500ml ether divides 2 extraction hydrolyzed solutions, extracting solution is through anhydrous magnesium sulfate drying, reclaim ether and obtain pale yellow oily liquid body 3-formyl benzofuran-2 (3H)-one.
Above-mentioned oily matter is dissolved in 150mlDMF, adds salt of wormwood 35g powder simultaneously, drips 26g methyl-sulfate under room temperature, after dropping terminates, continue insulation reaction 4 hours, add in 200ml water, 300ml ether divides three extraction hydrolyzed solutions, and suitable quantity of water washing ether extracted liquid, reclaims ether, add 30ml methyl alcohol, cooling crystallization, filters, obtains 31g pale yellow crystals 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, fusing point 100 ~ 101 DEG C, yield 88%.
Embodiment 6:
Control 20 ~ 25 DEG C, 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one 17.6g and 4, 6-dichloro pyrimidine 16.5g is dissolved in methyl-formiate 60ml under stirring, 28% sodium methylate 24.5g is dripped in 8 hours, after adding all sodium methoxide solutions, mixture is stirred 2 hours, reaction solution pH6 ~ 7 adjusted by appropriate acetic acid, then distillation removing low-boiling-point substance from reaction mixture, obtain residue, add toluene 100ml and water 100ml, stir the mixture at 50 DEG C 30 minutes, be separated organic phase and aqueous phase, organic phase reclaim under reduced pressure toluene, add 0.25g sal enixum at 140 DEG C of reaction 2h, obtain oily matter 25g, the wherein content 75% of (E)-2-[2-(6-chloropyrimide-4-oxygen base) phenyl]-3-methoxy propyl diluted acid methyl esters, yield 65%, do not refine and be directly used in the next step.
Control 85 ~ 95 DEG C, the mixed solution of dropping 2-cyanophenol 11.5g, salt of wormwood 8.7g and water 25ml is in the 25.0g mixture containing (E)-2-[2-(6-chloropyrimide-4-oxygen base) phenyl]-3-methoxy propyl diluted acid methyl esters, add rear intensification, constantly steam water, 130 DEG C are incubated 3 hours.Then this mixture is cooled to 70 DEG C, adds methyl alcohol 50ml, dissolve after 30 minutes and filter, filtrate is cooled to about 0 DEG C and keeps crystallization in 2 hours.Filter and namely obtain (E)-2-[2-(6-cyano-benzene oxygen pyrimidine-4-oxygen base) phenyl]-3-methoxy propyl diluted acid methyl esters, be Azoxystrobin, content 95%, productive rate 82.0%.
Claims (4)
1. prepare the method for Azoxystrobin for one kind, it is characterized in that, described method comprises the step generating Azoxystrobin: carry out formylation reaction in the presence of a catalyst by cumarone-2 (3H)-one and manthanoate, generate 3-formyl benzofuran-2 (3H)-one, the latter and methyl-sulfate carry out first oxidizing reaction and generate 3-(α-methoxyl group)-methylenebenzofuran-2 (3H)-one, again with 4, 6-dichloro pyrimidine and 2-cyanophenol react, generate Azoxystrobin, wherein: the mol ratio of reaction mass is: cumarone-2 (3H)-one: catalyzer: manthanoate: methyl-sulfate=1.0: 1.0 ~ 2.5: 1.0 ~ 10.0: 0.9 ~ 2.5, formylation reaction temperature-10 ~ 45 DEG C, 2 ~ 24 hours reaction times, first oxidizing reaction temperature 0 ~ 60 DEG C, 1 ~ 4 hour reaction times.
2. the method preparing Azoxystrobin according to claim 1, is characterized in that, described manthanoate is methyl-formiate or ethyl formate.
3. the method preparing Azoxystrobin according to claim 1, is characterized in that, described catalyzer is sodium salt or the sylvite of sodium hydride or alcohol.
4. the method preparing Azoxystrobin according to claim 3, it is characterized in that, the sodium salt of described alcohol or sylvite are sodium methylate/potassium methylate, sodium ethylate/potassium ethylate, sodium propylate/potassium propylate, sodium isopropylate/potassium isopropoxide, sodium butylate/butanols potassium or sodium tert-butoxide/potassium tert.-butoxide.
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| CN201410281550.5A CN105218461A (en) | 2014-06-20 | 2014-06-20 | A kind of method preparing Azoxystrobin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004234A (en) * | 2019-12-19 | 2021-06-22 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3-hydroxymethylene benzofuran-2 (3H) -one and azoxystrobin intermediate |
| CN113861116A (en) * | 2021-09-08 | 2021-12-31 | 安徽广信农化股份有限公司 | Synthesis process of pyraclostrobin |
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2014
- 2014-06-20 CN CN201410281550.5A patent/CN105218461A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004234A (en) * | 2019-12-19 | 2021-06-22 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3-hydroxymethylene benzofuran-2 (3H) -one and azoxystrobin intermediate |
| CN113861116A (en) * | 2021-09-08 | 2021-12-31 | 安徽广信农化股份有限公司 | Synthesis process of pyraclostrobin |
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Application publication date: 20160106 |