CN104387329A - Method for synthesizing intermediate methyl 2-(2-(6-chloropyrimidine-4-yl-oxo)phenyl) acetate - Google Patents
Method for synthesizing intermediate methyl 2-(2-(6-chloropyrimidine-4-yl-oxo)phenyl) acetate Download PDFInfo
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- CN104387329A CN104387329A CN201410610178.8A CN201410610178A CN104387329A CN 104387329 A CN104387329 A CN 104387329A CN 201410610178 A CN201410610178 A CN 201410610178A CN 104387329 A CN104387329 A CN 104387329A
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- 0 COC(Cc1ccccc1*)=O Chemical compound COC(Cc1ccccc1*)=O 0.000 description 2
- XHSWNFSJZXCZQS-UHFFFAOYSA-N COC(Cc1ccccc1Oc1ncnc(Cl)c1)=O Chemical compound COC(Cc1ccccc1Oc1ncnc(Cl)c1)=O XHSWNFSJZXCZQS-UHFFFAOYSA-N 0.000 description 1
- BBCUITRCMANRAV-UHFFFAOYSA-N I/[O]=C1\Oc2ccccc2C1 Chemical compound I/[O]=C1\Oc2ccccc2C1 BBCUITRCMANRAV-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
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Abstract
The invention relates to a method for preparing a compound of a structural formula (1) shown in the specification. The preparation method comprises the following steps: 1) carrying out a ring-opening esterification reaction between coumaranone and sodium methoxide so as to obtain a compound of a structural formula (2) shown in the specification; 2) enabling the compound of the structural formula (2) shown in the specification to react with 4,6-dichloropyrimidine so as to obtain a compound of a structural formula (3) shown in the specification; 3) preparing the compound of the structural formula (1) shown in the specification from the compound of the structural formula (3) shown in the specification, wherein the content is over 95.0 percent, and the highest yield is 96.0 percent; and a raw material hydroxyphenylacetic acid for synthesizing the compound of the structural formula (3) is not needed to be purified. The method is high in utilization rate of the raw materials for synthesizing, easy to operate, fewer in three wastes and low in process time consumption and is a synthetic method suitable for industrialization. According to the synthetic process, any catalyst is not used, the yield is high, and the utilization rate of 4,6-dichloropyrimidine is improved.
Description
Technical field
The present invention relates to agricultural bacteriocide E) new preparation process of-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, belong to pharmaceutical synthesis field.
Background technology
E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate (azoxystrobin) is the exploitation of prompt sharp Kanggong department and first commercial methoxy acrylic (β-methoxyacrylates) sterilant, and commodity are called Abound, Amistar, Heritage, Quadris, Admire.Since listing in 1997, be that global marketing volume is sure to occupy primary sterilant.E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate has that drug effect is high, toxicity is low, fungicidal spectrum is wide, advantages of environment protection, almost all has good activity to all mycota diseases.Can be used for various types of grain, fruits and vegetables.Therefore its synthetic method of a lot of patent literature is had, such as patent EP-A-0382375, CN 101157657A, WO92/08703A1, GB229174 etc.
E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate
The E of current bibliographical information)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate synthetic method mainly contains following several.
(1) o-hydroxy phenylacetic acid is starting raw material, trimethyl orthoformate or methyl-formiate is utilized to introduce methoxy methene on its side chain, then E is obtained with 4,6-dichloro pyrimidine and adjacent cyanophenol condensation successively)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate.This step reactions steps is more, and consuming time longer, aftertreatment is loaded down with trivial details, and wastewater flow rate is quite large.
(2) o-hydroxy phenylacetic acid is starting raw material, first utilizes benzyl protection phenolic hydroxyl group, then utilizes sodium methylate, and methyl-formiate carries out methoxy methyl olefination, more successively with 4,6-dichloro pyrimidine and adjacent cyanophenol condensation.Another kind of route of synthesis: take o-hydroxy phenylacetic acid as starting raw material, first utilize benzyl protection phenolic hydroxyl group, then utilize sodium methylate; methoxy methyl olefination is carried out with methyl-formiate; after 4,6-dichloro pyrimidine and adjacent cyanophenol condensation, then react with the intermediate that front step is reacted.
Above-mentioned two kinds of methods starting raw material o-hydroxy phenylacetic acid used needs to purify, and add the cost of technique, and solid waste is many, complex operation.
(3) o-hydroxy phenylacetic acid is starting raw material, under sulfur oxychloride exists, o-hydroxy phenylacetic acid and methanol esterification generate o-methyl hydroxyphenylacetate, this methyl esters is directly with 4, the condensation of 6-dichloro pyrimidine generates 2-(6-chloropyrimide-4 base oxygen base) methyl phenylacetate, this intermediate sodium hydride exist under with the position formylation of methyl-formiate generation benzyl, through aldehyde-tautomerism, methylate to obtain intermediate (E)-2-[2-(6-chloropyrimide-4-oxygen) phenyl]-3-methoxy-methyl acrylate, last and salicylonitrile condensation generates E)-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate.
This operational path is by E) synthesis of-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate shortens to 4 steps by 6 steps, and easy and simple to handle, total recovery can be increased to 50%.But this technique o-methyl hydroxyphenylacetate building-up process can increase very large wastewater flow rate, and post-processing step is loaded down with trivial details, if unreacted excessive methanol, unspent catalyzer sulfur oxychloride are with its hydrolysis gained hydrogenchloride, unreacted o-hydroxy phenylacetic acid etc., whole system is strongly-acid.So purify from this individual system obtain o-methyl hydroxyphenylacetate, need loaded down with trivial details post-processing step, and in treating processes, produce a large amount of waste water.
Therefore, also need to develop better synthetic route further, to simplify the operation, reduce and take liquid discharge, environment is more friendly.
Summary of the invention
The invention provides the novel processing step of a kind of structural formula (1) compound, this preparation method provides E) the another kind of synthetic method of-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate intermediate, for E) synthesis of-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate provides a kind of novel method, the method substantially reduces reaction times and post-processing step, for E) safety in production of-[2-[6-(2-cyano-benzene oxygen) pyrimidine-4-yl oxygen] phenyl]-3-methoxy-methyl acrylate provides a low consumption and the condition of safety.
The preparation method of described compound (1) comprising:
(1) in the organic solution of benzofuranone, drip sodium methylate, back flow reaction for some time disappears to benzofuranone and obtains structural formula (2) compound, reacts complete, cooling.
(2) in system, add 4,6-dichloro pyrimidine insulation reaction and obtain structural formula (1) compound.
(3) feed liquid in step (2), suction filtration desalination, obtains the solution of structural formula (1) compound.
(4) by the solution of structural formula (1) compound, after negative pressure has taken off solvent, after adding recrystallizing methanol, filter, dry and obtain structural formula (1) compound solid.
The concentration of the sodium methylate described in the present invention is 15-30%, consumption based on benzofuranone is 1.0-2.0 molar equivalent, 4, the consumption of 6-dichloro pyrimidine is 0.98-1.0 molar equivalent based on the consumption of benzofuranone, and the consumption of methyl alcohol is 1.0-3.0 mass equivalent based on the consumption of benzofuranone.
Organic solvent described in the present invention comprises the organic solvents such as methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, toluene, benzene, acetone, butanone, butylacetate, ethyl acetate.
Open loop alkaline hydrolysis temperature in described step (1) is more preferably in 0-100 DEG C, and in described step (2), setting-up point is more preferably in 0-30 DEG C, and in described step (4), precipitation temperature is more preferably in 50-120 DEG C.
The following example sets forth the present invention, but the present invention apply for protecting content and scope by the restriction of following embodiment.During embodiment illustrates, symbol g=gram, mL=milliliter, mol=mole, DEG C=degree Celsius.
Beneficial effect
1. present invention, avoiding treatment step loaded down with trivial details in o-methyl hydroxyphenylacetate building-up process, greatly simplify operation, decrease wastewater flow rate.
2. obtain structural formula (2) compound after benzofuranone open loop, without any need for catalyzer, impurity is few, and yield is high.
3. method of the present invention has that step is few, cost is low, adopts " one kettle way " to prepare, is very applicable to industrial production.
4. the present invention is just with benzofuranone, avoids the steps such as the hydroxyl protection of o-hydroxy phenylacetic acid, decreases synthesis step, decrease the generation of the three wastes, environmental friendliness.
Embodiment
Embodiment 1
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 260.0g methyl alcohol, be warming up to 60-70 DEG C, start the sodium methylate 181.8g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.0 hours.Subsequently, cool to 20-25 DEG C, add 148.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 5 hours, adds 1.2g30% hydrochloric acid, suction filtration, negative pressure deviates from solvent 187.0g, temperature rising reflux 0.5 hour, cools to 0-5 DEG C of insulation 2 hours, suction filtration, dry to obtain structural formula (1) compound 267.9g, content 97.6%, yield 96.2%.
Embodiment 2
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 165.0g methyl alcohol, be warming up to 60-65 DEG C, start the sodium methylate 272.7g of agitation and dropping 20.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.5 hours.Subsequently, cool to 25-30 DEG C, add 150.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 6 hours, and suction filtration, adds 1.2g30% hydrochloric acid, negative pressure deviates from methyl alcohol 183.0g, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain structural formula (1) compound 265.1g, content 96.9%, yield 95.2%.
Embodiment 3
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%108.3g benzofuranone and 300.0g toluene, be warming up to 65-70 DEG C, start the sodium methylate 157.0g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 3.5 hours.Subsequently, cool to 15-20 DEG C, add 118.0g4,6-dichloro pyrimidine, 15-20 DEG C is incubated 8 hours, and the hydrochloric acid adding 8.5g30% adjusts pH, filter, reduce pressure de-for solvent clean, cooling, add methyl alcohol 150g, temperature rising reflux about 0.5 hour, cools to 0-5 DEG C, suction filtration, dry to obtain structural formula (1) compound 196.7g, content 95.2%, yield 88.3%.
Embodiment 4
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 260.0g methyl alcohol, be warming up to 60-70 DEG C, start the sodium methylate 333.0g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.0 hours.Subsequently, cool to 20-25 DEG C, add 148.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 5 hours, adds 101.3g30% hydrochloric acid and adjusts pH, suction filtration, after solvent has been steamed in decompression, has added 160g methyl alcohol, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain structural formula (1) compound 200.1g, content 93.6%, yield 89.8%.
Embodiment 5
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%108.3g benzofuranone and 300.0g toluene, be warming up to 65-70 DEG C, start the sodium methylate 345.6g of agitation and dropping 20.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 3.5 hours.Subsequently, cool to 25-30 DEG C, add 118.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 8 hours, suction filtration, add 57.8g30% hydrochloric acid, negative pressure has taken off solvent, adds 150g methyl alcohol, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain structural formula (1) compound 206.1g, content 95.7%, yield 92.5%.
Embodiment 6
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%108.3g benzofuranone and 300.0g butanone, be warming up to 65-70 DEG C, start the sodium methylate 172.8g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 3.0 hours.Subsequently, cool to 20-25 DEG C, add 118.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 7 hours, adds 18.6g30% hydrochloric acid, suction filtration, negative pressure has taken off solvent, adds 150g methyl alcohol, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain structural formula (1) compound 207.6g, content 95.1%, yield 93.2%.
Embodiment 7
The preparation of structural formula (1) compound
In 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 260.0g methyl alcohol, be warming up to 60-70 DEG C, start the sodium methylate 198.0g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.0 hours.Subsequently, cool to 35-40 DEG C, add 148.0g4,6-dichloro pyrimidine, 35-40 DEG C is incubated 4 hours, adds 21.8g30% hydrochloric acid and adjusts pH, suction filtration, negative pressure has taken off solvent, adds methyl alcohol 180g, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain structural formula (1) compound 255.1g, content 92.9%, yield 91.6%.
Above-described embodiment is further described foregoing of the present invention, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to above-described embodiment.All technology realized based on foregoing all belong to scope of the present invention.
Claims (10)
1. the preparation method of synthetic intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, it is characterized in that: comprise the following steps: in the organic solution of benzofuranone, drip sodium methylate, back flow reaction disappears to benzofuranone and obtains structural formula (2) compound, react complete, cooling, 4 are added in solution, 6-dichloro pyrimidine insulation reaction obtains structural formula (1) compound, be 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate
2. preparation method according to claim 1, is characterized in that: the feed liquid in step (2), and suction filtration desalination obtains the solution of structural formula (1) compound.
3. preparation method according to claim 1, is characterized in that: by the solution of structural formula (1) compound, after negative pressure has taken off solvent, after adding recrystallizing methanol, filters, and dries and obtains structural formula (1) compound solid.
4. preparation method according to claim 1, is characterized in that: the organic solution of benzofuranone, and its organic solvent is methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, toluene, benzene, acetone, butanone, butylacetate or ethyl acetate.
5. preparation method according to claim 1, it is characterized in that: the concentration of described sodium methylate is 15-30%, consumption based on benzofuranone is 1.0-2.0 molar equivalent, 4, the consumption of 6-dichloro pyrimidine is 0.98-1.0 molar equivalent based on the consumption of benzofuranone, and the consumption of methyl alcohol is 1.0-3.0 mass equivalent based on the consumption of benzofuranone.
6. preparation method according to claim 1, it is characterized in that: the open loop alkaline hydrolysis temperature in described step (1) is more preferably in 0-100 DEG C, in described step (2), setting-up point is more preferably in 0-30 DEG C, and in described step (4), precipitation temperature is more preferably in 50-120 DEG C.
7. the preparation method of synthetic intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, it is characterized in that: comprise the following steps: in 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 260.0g methyl alcohol, be warming up to 60-70 DEG C, start the sodium methylate 181.8g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.0 hours.Subsequently, cool to 20-25 DEG C, add 148.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 5 hours, adds 1.2g30% hydrochloric acid, suction filtration, negative pressure deviates from solvent 187.0g, temperature rising reflux 0.5 hour, cools to 0-5 DEG C of insulation 2 hours, suction filtration, dry to obtain 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate 267.9g, content 97.6%, yield 96.2%.
8. the preparation method of synthetic intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, it is characterized in that: comprise the following steps: in 1000mL four-hole bottle, add 99.0%135.4g benzofuranone and 165.0g methyl alcohol, be warming up to 60-65 DEG C, start the sodium methylate 272.7g of agitation and dropping 20.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 1.5 hours.Subsequently, cool to 25-30 DEG C, add 150.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 6 hours, and suction filtration, adds 1.2g30% hydrochloric acid, negative pressure deviates from methyl alcohol 183.0g, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate 265.1g, content 96.9%, yield 95.2%.
9. the preparation method of synthetic intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, it is characterized in that: comprise the following steps: in 1000mL four-hole bottle, add 99.0%108.3g benzofuranone and 300.0g butanone, be warming up to 65-70 DEG C, start the sodium methylate 172.8g of agitation and dropping 30.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 3.0 hours.Subsequently, cool to 20-25 DEG C, add 118.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 7 hours, adds 18.6g30% hydrochloric acid, suction filtration, negative pressure has taken off solvent, adds 150g methyl alcohol, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate 207.6g, content 95.1%, yield 93.2%.
10. the preparation method of synthetic intermediate 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate, it is characterized in that: comprise the following steps: in 1000mL four-hole bottle, add 99.0%108.3g benzofuranone and 300.0g toluene, be warming up to 65-70 DEG C, start the sodium methylate 345.6g of agitation and dropping 20.0%, drip 1.5 hours altogether, dropwise 65-70 DEG C and continue insulation 3.5 hours.Subsequently, cool to 25-30 DEG C, add 118.0g4,6-dichloro pyrimidine, 20-25 DEG C is incubated 8 hours, suction filtration, add 57.8g30% hydrochloric acid, negative pressure has taken off solvent, adds 150g methyl alcohol, temperature rising reflux 0.5 hour, cool to 0-5 DEG C of insulation 2 hours, suction filtration, dries to obtain 2-(2-(6-chloropyrimide-4-base oxygen) phenyl) methyl acetate 206.1g, content 95.7%, yield 92.5%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083735A (en) * | 2016-06-03 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of synthesis technique of azoxystrobin intermediate |
| CN113105496A (en) * | 2021-03-19 | 2021-07-13 | 华南理工大学 | Method for synthesizing o-alkenylphenol derivative through nickel-catalyzed ring opening of benzofuran |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012416A (en) * | 2001-07-04 | 2003-01-15 | Nissan Chem Ind Ltd | Microbicidal insecticide agent for agriculture and horticulture including phenyl acetic acid derivatives |
| CN101723905A (en) * | 2009-11-25 | 2010-06-09 | 大连凯飞精细化工有限公司 | Synthesis method of 2-(2-(6-(2-cyano phenoxyl) pyridine-4-oxygroup) phenyl) methyl acetate |
| CN103724203A (en) * | 2014-01-28 | 2014-04-16 | 重庆紫光化工股份有限公司 | Preparation method of o-methyl hydroxyphenylacetate |
-
2014
- 2014-10-27 CN CN201410610178.8A patent/CN104387329A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003012416A (en) * | 2001-07-04 | 2003-01-15 | Nissan Chem Ind Ltd | Microbicidal insecticide agent for agriculture and horticulture including phenyl acetic acid derivatives |
| CN101723905A (en) * | 2009-11-25 | 2010-06-09 | 大连凯飞精细化工有限公司 | Synthesis method of 2-(2-(6-(2-cyano phenoxyl) pyridine-4-oxygroup) phenyl) methyl acetate |
| CN103724203A (en) * | 2014-01-28 | 2014-04-16 | 重庆紫光化工股份有限公司 | Preparation method of o-methyl hydroxyphenylacetate |
Non-Patent Citations (1)
| Title |
|---|
| 董捷等: "嘧菌酯的合成", 《精细化工中间体》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083735A (en) * | 2016-06-03 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of synthesis technique of azoxystrobin intermediate |
| CN106083735B (en) * | 2016-06-03 | 2018-09-21 | 安徽广信农化股份有限公司 | A kind of synthesis technology of azoxystrobin intermediate |
| CN113105496A (en) * | 2021-03-19 | 2021-07-13 | 华南理工大学 | Method for synthesizing o-alkenylphenol derivative through nickel-catalyzed ring opening of benzofuran |
| CN113105496B (en) * | 2021-03-19 | 2022-06-14 | 华南理工大学 | Method for synthesizing o-alkenylphenol derivative through nickel-catalyzed ring opening of benzofuran |
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