CN106810502A - A kind of preparation method of azoxystrobin intermediate - Google Patents
A kind of preparation method of azoxystrobin intermediate Download PDFInfo
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- CN106810502A CN106810502A CN201510860484.1A CN201510860484A CN106810502A CN 106810502 A CN106810502 A CN 106810502A CN 201510860484 A CN201510860484 A CN 201510860484A CN 106810502 A CN106810502 A CN 106810502A
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- piperazine
- divinyl
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- alkyl
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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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- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of azoxystrobin intermediate, efficient synthesis azoxystrobin intermediate by the way of adding catalyst in open loop, etherification reaction specifically includes following steps：Methoxy methylenebenzofuran ketone and dichloro pyrimidine addition sodium methoxide/methanol solution under conditions of catalyst presence carry out open loop, etherification reaction synthesis azoxystrobin intermediate compound B.Compared with prior art, the present invention has the advantages that efficiency high, yield are high.
Description
Technical field
The present invention relates to a kind of preparation of pesticide intermediate, more particularly, to a kind of new method for efficiently preparing azoxystrobin intermediate.
Background technology
Fluoxastrobin is the maximum disinfectant use in agriculture product in the whole world at present, wide spectrum, efficiently, is produced and used extensively.In the middle of the key of Fluoxastrobin
Body compound B synthesis is general first phonetic with 4,6- dichloros in sodium methoxide/methanol solution by methoxy methylenebenzofuran ketone (compound A)
Pyridine carries out open loop, etherification reaction and obtains.Domestic majority enterprise is closed using the method as described in patent CN1062139A by compound A now
Into to compound B, being added without being directly added into sodium methoxide open loop, etherification reaction under conditions of any catalyst, but its yield can be only sustained at
60~70% or so, reaction produces substantial amounts of accessory substance, directly influences the purifying of product in subsequent step.
Azoxystrobin intermediate B is the very crucial intermediate for synthesizing Fluoxastrobin, and current most domestic company is using the special of Syngenta Co., Ltd
The method of sharp CN1062139A description be in organic solvent by compound A and dichloro pyrimidine at low temperature, be slowly added dropwise into sodium methoxide/first
Alcoholic solution realizes continuous open loop, the etherificate of compound A and dichloro pyrimidine, and the subject matter that the method is present is：1) reaction time compared with
Length is, it is necessary to react 22 hours, it is larger that this causes the step to react the energy consumption for producing；2) the method yield is relatively low, and yield is only capable of reaching 60~
70% or so；3) impurity for producing is difficult to purify, and influences product purity；4) cause production cost higher because the yield of the method is relatively low.
The present invention is greatly to accelerate this by adding divinyl piperazines catalyst during open loop, etherificate with patent CN1062139A differences
Step reaction, it is only necessary to reaction can be terminated in 5 hours, and yield is improved to 80~90%, greatly reduces the refined difficulty in subsequent handling
Degree, reduces production cost.
The content of the invention
The purpose of the present invention be exactly provide that a kind of reaction time is short for the defect for overcoming above-mentioned prior art to exist, in the middle of high income Fluoxastrobin
The preparation method of body.
The purpose of the present invention can be achieved through the following technical solutions：A kind of preparation method of azoxystrobin intermediate, it is characterised in that use
To the efficient synthesis azoxystrobin intermediate of mode that catalyst is added in open loop, etherification reaction, following steps are specifically included：By methoxy methylene
Base benzofuranone (compound A) and dichloro pyrimidine addition sodium methoxide/methanol solution under conditions of catalyst presence carry out open loop, etherification reaction
Synthesis azoxystrobin intermediate compound B.
Described catalyst includes the compound with following structural formula：
Wherein R1, R3, R5, R6 is H, halogen, C1-C10 oxygen-containing or not oxygen-containing aliphatic group or aryl, R2 and
R4 is halogen, C1-C10 is oxygen-containing or not oxygen-containing aliphatic group or aryl, ester group.
Described catalyst be 2- alkyl or alkoxy divinyl piperazine, 2- aryl divinyls piperazine, 2- alkyl or alkoxy -2 '-alkyl or
Alkoxy (C1-C10) divinyl piperazine, 2,3- dialkyl group or alkoxy (C1-C4) divinyl piperazine, 2,5- dialkyl group
Or alkoxy (C1-C4) or diaryl divinyl piperazine, 2,6- dialkyl group or alkoxy (C1-C4) or diaryl divinyl piperazine, 2-
One or more in ester group (C2-C5) divinyl piperazine：
Wherein alkyl or alkoxy include methyl, ethyl, propyl group, butyl, defend base, hexyl, heptyl, octyl group, nonyl, or its
Oxygen-containing group；Aryl includes phenyl or substituted-phenyl；Ester group includes methyl formate base, group-4 ethyl formate, methyl acetate base, ethyl acetate
Base；The wherein preferred methyl of 2- alkyl or ethyl.
The consumption of described catalyst is：The mol ratio of compound A and catalyst is 1: 0.002~0.078.
Described open loop, etherification reaction is carried out in a solvent, and described solvent includes that aromatic hydrocarbons, ethers, nitrile, amide-type or esters are molten
Agent.
Described open loop, the reaction temperature of etherification reaction are -20~50 DEG C.
Described open loop, the reaction temperature of etherification reaction are 0~30 DEG C.
Compared with prior art, the present invention uses divinyl piperazine compounds as catalyst first, for catalytic cpd A and 4,6-
Dichloro pyrimidine carries out the key intermediate B that open loop, etherification reaction obtain Fluoxastrobin, and the total recovery of step reaction reaches 80-90%, compares prior art
Improve 10~20% and more than, production cost can be reduced by a relatively large margin, improve the purity of intermediate B so that final products Fluoxastrobin
Purifying is easier.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Put into successively in 500 milliliters of there-necked flasks 46.6 g of compound A (98%, 0.26mol), 46.6 grams of dichloro pyrimidines (98.5%,
0.308mol) with 130 milliliters of tetrahydrofurans, stir at room temperature, then put into 0.4 gram of 2- methyl divinyls piperazine, stirring is cooled to
15 DEG C start to be added dropwise to 53.8 grams of methanol solutions of sodium methoxide (28.87%, 0.287mol), and time for adding is controlled 5 hours, after completion of dropwise addition
20 DEG C are incubated 1 hour.Add 36% hydrochloric acid to be acidified to PH=4, add water agitator treating 2 times, and precipitation obtains crude compound B, receive
Rate 80%.
Embodiment 2
46.6 g of compound A (98%, 0.26mol), 130 milliliters of acetonitriles are put into 500 milliliters of there-necked flasks successively, stirs equal at room temperature
It is even, then put into 0.4 gram of 2- methyl divinyls piperazine, stirring be cooled to 15 DEG C start to be added dropwise to 53.8 grams of methanol solutions of sodium methoxide (28.87%,
0.287mol), time for adding control half an hour, after completion of dropwise addition 20 DEG C be incubated 1 hour, be subsequently adding 46.6 grams of dichloro pyrimidines (98.5%,
0.308mol).Insulation adds 36% hydrochloric acid to be acidified to PH=4 after 1 hour, and add water agitator treating 2 times, and it is thick that precipitation obtains compound B
Product, yield 85%.
Claims (2)
1. a kind of preparation method of azoxystrobin intermediate, it is characterised in that efficient by the way of adding catalyst in open loop, etherification reaction
Synthesis azoxystrobin intermediate, specifically includes following steps：The bar existed in catalyst by methoxy methylenebenzofuran ketone and dichloro pyrimidine
Sodium methoxide/methanol solution is added under part carries out open loop, etherification reaction synthesis Fluoxastrobin intermediate compound B.
2. the preparation method of a kind of azoxystrobin intermediate according to claim 1, it is characterised in that described catalyst is 2- alkyl or alcoxyl
Base divinyl piperazine, 2- aryl divinyls piperazine, 2- alkyl or alkoxy -2 '-alkyl or alkoxy (C1-C10) divinyl piperazine
Piperazine, 2,3- dialkyl group or alkoxy (C1-C4) divinyl piperazine, 2,5- dialkyl group or alkoxy (C1-C4) or diaryl
Divinyl piperazine, 2,6- dialkyl group or alkoxy (C1-C4) or diaryl divinyl piperazine, 2- ester groups (C2-C5) divinyl
One or more in piperazine；Wherein alkyl or alkoxy include methyl, ethyl, propyl group, butyl, defend base, hexyl, heptyl, octyl group,
Nonyl, or and its oxygen-containing group；Aryl includes phenyl or substituted-phenyl；Ester group includes methyl formate base, group-4 ethyl formate, methyl acetate
Base, ethyl acetate base；The wherein preferred methyl of 2- alkyl or ethyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510860484.1A CN106810502A (en) | 2015-11-29 | 2015-11-29 | A kind of preparation method of azoxystrobin intermediate |
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| CN201510860484.1A CN106810502A (en) | 2015-11-29 | 2015-11-29 | A kind of preparation method of azoxystrobin intermediate |
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| CN201510860484.1A Pending CN106810502A (en) | 2015-11-29 | 2015-11-29 | A kind of preparation method of azoxystrobin intermediate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721545A (en) * | 2017-10-31 | 2019-05-07 | 南通泰禾化工股份有限公司 | A kind of preparation method of azoxystrobin intermediate |
| CN115557901A (en) * | 2022-10-21 | 2023-01-03 | 湖北有宜新材料科技有限公司 | Efficient production method of pyrimidofuranone |
-
2015
- 2015-11-29 CN CN201510860484.1A patent/CN106810502A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721545A (en) * | 2017-10-31 | 2019-05-07 | 南通泰禾化工股份有限公司 | A kind of preparation method of azoxystrobin intermediate |
| CN115557901A (en) * | 2022-10-21 | 2023-01-03 | 湖北有宜新材料科技有限公司 | Efficient production method of pyrimidofuranone |
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Application publication date: 20170609 |