CN102311392A - Synthetic method of azoxystrobin and special intermediate for synthesis - Google Patents
Synthetic method of azoxystrobin and special intermediate for synthesis Download PDFInfo
- Publication number
- CN102311392A CN102311392A CN201110244816A CN201110244816A CN102311392A CN 102311392 A CN102311392 A CN 102311392A CN 201110244816 A CN201110244816 A CN 201110244816A CN 201110244816 A CN201110244816 A CN 201110244816A CN 102311392 A CN102311392 A CN 102311392A
- Authority
- CN
- China
- Prior art keywords
- reaction
- toluene
- distillation
- described step
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The invention relates to a synthetic process of a chemical substance, and particularly relates to a synthetic method for synthesizing (E)-2-[2-(6-chloro pyrimidine-4-yloxy)phenyl]-3-methoxy methacrylate and azoxystrobin; the method comprises the following steps: mixing a raw material of 3-(alpha-methoxy)methylene benzofuran-2-(3H)-ketone and potassium carbonate in a toluene solvent, cooling to 0-10 DEG C, adding sodium methoxide, reacting for 0.4-0.6 hours; adding 4,6-dichloropyrimidine and a catalyst of DABCO, reacting for 1-2 hours, filtering to remove inorganic salts, washing the filtrate with water, performing distillation to recover toluene; adding a catalyst of potassium bisulfate into the distillation residues of the above reaction, heating to 132-145 DEG C in a reduced-pressure condition for reaction; directly adding salicylonitrile to synthesize azoxystrobin or performing toluene dissolution, water washing, solvent recovery, recrystallization and filtration to obtain an intermediate. The production and synthesis of (E)-2-[2-(6-chloro pyrimidine-4-yloxy)phenyl]-3-methoxy methacrylate by the production process of the invention has high yield, and simple operations, and the used raw materials and processes are routine reagents and methods.
Description
Technical field
The present invention relates to a kind of synthesis technique of chemical substance, be specifically related to synthesize the method for (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate; And utilize this material finally to synthesize the method for ICIA 5504.
Background technology
(E)-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-the 3-methoxy-methyl acrylate is an important midbody of synthetic ICIA 5504 to 2-.The method synthesis technique of existing (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate mainly is:
1, one kettle way: with 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone is starting raw material, and with sodium methylate and 4,6-2 dichloro pyrimidine (DCP) adopts one kettle way synthetic, this method long (about 50h) consuming time.Reaction formula is:
Side reaction mainly is:
The shortcoming of this compound method is: 1) reaction times oversize, and yield is low; 2) by product is many.
2, the method for fractional steps: the principal reaction formula is:
Its shortcoming is:
1, step is many, complex operation;
2, sodium methylate is excessive in a large number, raw material: sodium methylate=1: 4, and Atom economy is poor; Excessive sodium methylate needs not only to consume lot of organic acids with the acetic acid neutralization, also can produce the solid waste sodium acetate;
3, the excessive sodium methylate of neutralization need carry out (20 ℃) at low temperatures, and energy consumption is high;
4, in and the gained open-loop products need organic solvent extraction, washing, drying, a plurality of operation stepss of recovery solvent;
5, need to consume salt of wormwood and DMF, produce solid giving up, product needs organic solvent extraction, washing, drying, a plurality of operation stepss of recovery solvent;
6, open-loop products easy closed loop under acidic conditions gets by product, and corresponding side reaction is:
Not only reduce the yield of product, and increased the purifying difficulty of product, reduced production efficiency.
Summary of the invention
Main purpose of the present invention provides the method for a kind of synthetic (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate, and this method is simple to operate, can significantly improve the yield of product and shorten generated time.
The technical scheme that the present invention taked is: the method for a kind of synthetic (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate, and step comprises:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone and salt of wormwood are mixed in the toluene solvant, are cooled to 0-10 ℃, add sodium methylate, reacted 0.4～0.6 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine and catalyzer DABCO, reaction 1-2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards go on foot adding catalyst sulfuric acid hydrogen potassium in the reaction distillation resistates, be heated to 132～145 ℃ of reactions under the decompression state;
D: reaction system is removed the water solubles such as inorganic salt with toluene dissolving, washing, toluene solvant is reclaimed in distillation then, dissolved behind the thick product impurity screening liquid phase cools recrystallization with butylacetate then and filter and obtain target product.
Utilize production technique of the present invention to produce the yield height of synthetic (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate, and simple to operate, and employed raw material, technology all are conventional reagent and method.
Adding sodium methylate among the step a can be to add methanol solution of sodium methylate, also can be to add solid sodium methylate and methyl alcohol.And the weak base that is added among the step a (like salt of wormwood) guarantees that ring-opening reaction is in alkaline atmosphere all the time, avoids open-loop products to produce by product in closure.Add catalyzer DABCO coupling reaction is accomplished fast, shortened the reaction times greatly.PT can be controlled in 10 hours like this, and production efficiency significantly improves.
Further, among the described step c, detect in the reaction system coupled product content and be reaction end less than 1%.This moment, title product content can reach more than 80%, and the finished product yield is more than 70%.And farthest saved the PT again.
Further, among the described step a, cooling temperature is 8 ℃, and the reaction times is 0.5 hour.Cooling temperature is the cooling temperature of common used in industry cooling apparatus, is convenient to coordinative composition of equipments; The preferred time be the time value that can guarantee that technic index is simultaneously most economical again.In like manner, among the described step b, the reaction times is 1.5 hours.Among the described step c, Heating temperature is 140 ℃.The speed and the transformation efficiency of reaction have outstanding effect under this temperature condition.
The main chemical reactions formula of producing is:
Another object of the present invention provides a kind of supporting above-mentioned synthetic (E)-2-[2-(6-chloropyrimide-4-base oxygen base) the phenyl]-method of 3-methoxy-methyl acrylate and produces the method for ICIA 5504; Make that the synthesis technique of ICIA 5504 is simple, can significantly improve the yield and shortening generated time of product.
The technical scheme of being taked is: a kind of compound method of ICIA 5504, and step comprises:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone and salt of wormwood are mixed in the toluene solvant, are cooled to 0-10 ℃, add sodium methylate, reacted 0.4～0.6 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine and catalyzer DABCO, reaction 1-2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards go on foot adding catalyst sulfuric acid hydrogen potassium in the reaction distillation resistates, be heated to 132～145 ℃ of reactions under the decompression state;
D: in system, directly add the synthetic ICIA 5504 of salicylonitrile then.
Visible by technique scheme, obtained a large amount of (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate midbody among the step c.Add salicylonitrile then and can obtain ICIA 5504.Separate again and purify and to obtain the ICIA 5504 end product.Save the recrystallization and the lock out operation of midbody like this, realized collective effect, saved PT and raw material, energy consumption cost.Synthetic separation and purification with ICIA 5504 as for midbody and salicylonitrile has a variety of embodiments, itself is not inventive point of the present invention, so repeat no more.
Further, among the described step c, detect in the reaction system coupled product content and be reaction end, carry out the operation of steps d then less than 1%.The amount of (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate can reach more than 80% in the system at this moment, and the also corresponding maximum of product yield of synthetic ICIA 5504 has farthest been saved the PT again simultaneously.
In like manner, synthetic similar with midbody, among the described step a, cooling temperature is 8 ℃, the reaction times is 0.5 hour.Cooling temperature is the cooling temperature of common used in industry cooling apparatus, is convenient to coordinative composition of equipments; The preferred time be the time value that can guarantee that technic index is simultaneously most economical again.In like manner, among the described step b, the reaction times is 1.5 hours.Among the described step c, Heating temperature is 140 ℃.The speed and the transformation efficiency of reaction have outstanding effect under this temperature condition.
Improvement of the present invention is the improvement of technological process and controlling index; As for the charging capacity of proportioning raw materials, catalyzer etc. then is according to Theoretical Calculation or confirmable with reference to prior art; Not technological improvement of the present invention place, be not described in detail for practicing thrift length.
Embodiment
For making those skilled in the art's detail knowledge production technique of the present invention and technique effect, come further to introduce application of the present invention and technique effect with concrete production instance below.
Embodiment one
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.1mol and salt of wormwood 0.05mol are mixed in the 80mL toluene solvant; 0 ℃ of cooling temperature; The methanol solution of sodium methylate 21.2g (containing sodium methylate 0.11mol) of adding 28% reacted 0.4 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.11mol and catalyzer DABCO1.7g, reaction 1h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards go on foot in the distillation residue and to add catalyst sulfuric acid hydrogen potassium 1.5g, under-0.05MPa, be heated to 132 ℃ of reactions 1.5 hours, cool.
D: will go up the step reaction mixture with toluene dissolving, washing, recovery toluene solvant; Dissolve thick product recrystallization filtration with butylacetate then and obtain (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 22.8g, product yield 71.1%.Detect through HPLC, product purity is 98.6%.
Embodiment two
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.1mol and salt of wormwood 0.1mol are mixed in the 80mL toluene solvant, 5 ℃ of cooling temperatures, the methanol solution of sodium methylate 21.2g (containing sodium methylate 0.11mol) of adding 28% reacted 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.11mol and catalyzer DABCO1.7g, reaction 1.2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 1.5g, under-0.04MPa, be heated to 138 ℃ of reactions, is 0.85% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: will go up the step reaction mixture with toluene dissolving, washing, recovery toluene solvant; Dissolve thick product recrystallization filtration with butylacetate then and obtain (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 23.6g, product yield 73.6%.Detect through HPLC, product purity is 99.5%.
Embodiment three
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.1mol and salt of wormwood 0.1mol are mixed in the 100mL toluene solvant, and 8 ℃ of cooling temperatures successively add sodium methylate 0.11mol, methyl alcohol 10mL, react 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.11mol and catalyzer DABCO2.0g, reaction 1.5h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 1.5g, under-0.03MPa, be heated to 140 ℃ of reactions, is 0.9% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: reaction system with toluene dissolving, washing, recovery toluene solvant, is dissolved thick product recrystallization filtration with butylacetate then and obtained (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 25.0g, product yield 78.0%.Detect through HPLC, product purity is 99.7%.
Embodiment four
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.1mol and salt of wormwood 0.1mol are mixed in the 100mL toluene solvant, and 5 ℃ of cooling temperatures successively add sodium methylate 0.11mol, methyl alcohol 10mL, react 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.11mol and catalyzer DABCO2.0g, reaction 1.5h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 1.5g, under-0.03MPa, be heated to 140 ℃ of reactions, is 0.86% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: reaction system with toluene dissolving, washing, recovery toluene solvant, is dissolved thick product recrystallization filtration with butylacetate then and obtained (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 25.42g, product yield 79.3%.Detect through HPLC, product purity is 99.7%.
Visible by embodiment three, four, among the step a, successively add sodium methylate, methyl alcohol, cooperate other preferred processing condition, productive rate and product purity have unexpected significantly improving.
Embodiment five
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.1mol and salt of wormwood 0.1mol are mixed in the 80mL toluene solvant, 8 ℃ of cooling temperatures, the methanol solution of sodium methylate 21.2g (containing sodium methylate 0.11mol) of adding 28% reacted 0.6 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.11mol and catalyzer DABCO1.7g, reaction 2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 1.7g, under-0.1MPa, be heated to 140 ℃ of reactions, is 0.83% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: reaction system with toluene dissolving, washing, recovery toluene solvant, is dissolved thick product recrystallization filtration with butylacetate then and obtained (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 23.2g, product yield 72.4%.Detect through HPLC, product purity is 98.7%.
Embodiment six
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.2mol and salt of wormwood 0.22mol are mixed in the 150mL toluene solvant; 10 ℃ of cooling temperatures; Add 28% methanol solution of sodium methylate 42.4g (containing sodium methylate 0.22mol), reacted 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine and catalyzer DABCO3.4g, reaction 1.5h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 3.0g, under-0.02MPa, be heated to 145 ℃ of reactions, is 0.92% to be reaction end until using the HPLC method to detect in the reaction system coupled product content;
D: reaction system with toluene dissolving, washing, recovery toluene solvant, is dissolved thick product recrystallization filtration with butylacetate then and obtained (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate 47.5g, product yield 74.1%.Detect through HPLC, product purity is 97.6%.
Embodiment seven
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.2mol and salt of wormwood 0.22mol are mixed in the 150mL toluene solvant, and 8 ℃ of cooling temperatures add 28% methanol solution of sodium methylate 42.4g (containing sodium methylate 0.22mol), react 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.22mol and catalyzer DABCO3.4g, reaction 1.5h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 3.0g, under-0.03MPa, be heated to 140 ℃ of reactions, is 0.9% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: in system, directly add the synthetic ICIA 5504 of salicylonitrile then, separation and purification obtains ICIA 5504 product 52.6g, ICIA 5504 product yield 65.2%.Detect through HPLC, the ICIA 5504 product purity is 96.9%.
Embodiment eight
Step is:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone 0.2mol and salt of wormwood 0.22mol are mixed in the 150mL toluene solvant, and 8 ℃ of cooling temperatures add 28% methanol solution of sodium methylate 42.4g (containing sodium methylate 0.22mol), react 0.5 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine 0.22mol and catalyzer DABCO3.4g, reaction 1.5h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards going on foot in the reaction distillation resistates and to add catalyst sulfuric acid hydrogen potassium 3.0g, under-0.03MPa, be heated to 140 ℃ of reactions, is 0.8% to be reaction end until using HPLC to detect in the reaction system coupled product content;
D: in system, directly add the synthetic ICIA 5504 of salicylonitrile then, separation and purification obtains ICIA 5504 product 54.4g, ICIA 5504 product yield 67.5%.Detect through HPLC, the ICIA 5504 product purity is 97.7%.
Claims (10)
1. the method for synthetic (E)-2-[2-(6-chloropyrimide-4-base oxygen base) phenyl]-3-methoxy-methyl acrylate, step comprises:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone and salt of wormwood are mixed in the toluene solvant, are cooled to 0-10 ℃, add sodium methylate, reacted 0.4～0.6 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine and catalyzer DABCO, reaction 1-2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards go on foot adding catalyst sulfuric acid hydrogen potassium in the reaction distillation resistates, be heated to 132～145 ℃ of reactions under the decompression state;
D: reaction system is removed the water solubles such as inorganic salt with toluene dissolving, washing, toluene solvant is reclaimed in distillation then, dissolved behind the thick product impurity screening liquid phase cools recrystallization with butylacetate then and filter and obtain target product.
2. method according to claim 1 is characterized in that: among the described step c, detect in the reaction system coupled product content and be reaction end less than 1%.
3. method according to claim 1 and 2 is characterized in that: among the described step a, cooling temperature is 8 ℃, and the reaction times is 0.5 hour.
4. method according to claim 1 and 2 is characterized in that: among the described step b, the reaction times is 1.5 hours.
5. method according to claim 1 and 2 is characterized in that: among the described step c, Heating temperature is 140 ℃.
6. the compound method of an ICIA 5504, step comprises:
A: raw material 3-(α-methoxyl group) methylene radical benzo furans-2-(3H)-ketone and salt of wormwood are mixed in the toluene solvant, are cooled to 0-10 ℃, add sodium methylate, reacted 0.4～0.6 hour;
B: upwards go on foot and add 4 in the reaction solution, 6-dichloro pyrimidine and catalyzer DABCO, reaction 1-2h removes by filter inorganic salt, the filtrating washing, toluene is reclaimed in distillation;
C: upwards go on foot adding catalyst sulfuric acid hydrogen potassium in the reaction distillation resistates, be heated to 132～145 ℃ of reactions under the decompression state;
D: in system, directly add the synthetic ICIA 5504 of salicylonitrile then.
7. method according to claim 6 is characterized in that: among the described step c, detect in the reaction system coupled product content and be reaction end less than 1%.
8. according to claim 6 or 7 described methods, it is characterized in that: among the described step a, cooling temperature is 8 ℃, and the reaction times is 0.5 hour.
9. according to claim 6 or 7 described methods, it is characterized in that: among the described step b, the reaction times is 1.5 hours.
10. according to claim 6 or 7 described methods, it is characterized in that: among the described step c, Heating temperature is 140 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244816.5A CN102311392B (en) | 2011-08-24 | 2011-08-24 | Synthetic method of azoxystrobin and special intermediate for synthesis |
| PCT/CN2012/080434 WO2013026391A1 (en) | 2011-08-24 | 2012-08-21 | Synthesis method of azoxystrobin and exclusive intermediate in the synthesis thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110244816.5A CN102311392B (en) | 2011-08-24 | 2011-08-24 | Synthetic method of azoxystrobin and special intermediate for synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102311392A true CN102311392A (en) | 2012-01-11 |
| CN102311392B CN102311392B (en) | 2014-01-22 |
Family
ID=45424995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110244816.5A Expired - Fee Related CN102311392B (en) | 2011-08-24 | 2011-08-24 | Synthetic method of azoxystrobin and special intermediate for synthesis |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102311392B (en) |
| WO (1) | WO2013026391A1 (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013026391A1 (en) * | 2011-08-24 | 2013-02-28 | 重庆紫光化工股份有限公司 | Synthesis method of azoxystrobin and exclusive intermediate in the synthesis thereof |
| CN103265496A (en) * | 2013-05-16 | 2013-08-28 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| CN103467387A (en) * | 2013-09-05 | 2013-12-25 | 北京颖泰嘉和生物科技有限公司 | Method of preparing azoxystrobin and intermediate thereof |
| WO2014146581A1 (en) * | 2013-03-20 | 2014-09-25 | 北京颖泰嘉和生物科技有限公司 | Method for preparing acrylate compound |
| CN104230820A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230821A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230819A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230822A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104725321A (en) * | 2013-12-20 | 2015-06-24 | 上海泰禾化工有限公司 | Preparation method of azoxystrobin intermediate |
| CN107602480A (en) * | 2017-09-07 | 2018-01-19 | 连云港立本作物科技有限公司 | The preparation method of Fluoxastrobin |
| CN108516962A (en) * | 2018-05-21 | 2018-09-11 | 帕潘纳(北京)科技有限公司 | A kind of preparation method of azoxystrobin intermediate |
| US10150741B1 (en) | 2017-10-31 | 2018-12-11 | Cac Nantong Chemical Co., Ltd | Method for preparing azoxystrobin intermediates |
| WO2020212919A1 (en) * | 2019-04-18 | 2020-10-22 | Upl Limited | Process for preparation of azoxystrobin and intermediates thereof |
| CN112174897A (en) * | 2020-09-18 | 2021-01-05 | 广东石油化工学院 | Preparation method of azoxystrobin intermediate |
| CN114685375A (en) * | 2020-12-28 | 2022-07-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of [2- (6-chloropyrimidine-4-oxygen) phenyl ] -3, 3-dimethoxyacrylic acid methyl ester |
| CN114685376A (en) * | 2020-12-28 | 2022-07-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of azoxystrobin intermediate |
| CN114957134A (en) * | 2022-05-26 | 2022-08-30 | 安徽广信农化股份有限公司 | Method for preparing azoxystrobin and intermediate thereof |
| CN116120241A (en) * | 2023-02-27 | 2023-05-16 | 江苏快达农化股份有限公司 | Method for synthesizing azoxystrobin intermediate by using composite catalyst |
| US11952350B2 (en) | 2019-04-18 | 2024-04-09 | Upl Ltd. | Process for the preparation of fungicidally active strobilurin compounds and intermediates thereof |
| US12024492B2 (en) | 2019-04-18 | 2024-07-02 | Upl Ltd | Process for preparation of azoxystrobin and intermediates thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974097B (en) * | 2015-05-29 | 2018-04-17 | 重庆紫光化工股份有限公司 | A kind of synthetic method of Fluoxastrobin |
| CN105396349B (en) * | 2015-11-24 | 2024-05-14 | 重庆欣欣向荣精细化工有限公司 | Filter device for ethyl vanillin |
| CN110294716B (en) * | 2018-03-23 | 2021-05-07 | 帕潘纳(北京)科技有限公司 | Preparation method of azoxystrobin and intermediate thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062139A (en) * | 1990-11-16 | 1992-06-24 | 帝国化学工业公司 | The method for preparing phenoxyprimidine compounds |
| GB2291874A (en) * | 1994-07-28 | 1996-02-07 | Zeneca Ltd | Etherification process |
| CN101522639A (en) * | 2006-10-09 | 2009-09-02 | 先正达有限公司 | Preparation of azoxystrobin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311392B (en) * | 2011-08-24 | 2014-01-22 | 重庆紫光化工股份有限公司 | Synthetic method of azoxystrobin and special intermediate for synthesis |
| CN102399195A (en) * | 2011-12-08 | 2012-04-04 | 北京颖新泰康国际贸易有限公司 | Method for synthesizing azoxystrobin intermediate |
-
2011
- 2011-08-24 CN CN201110244816.5A patent/CN102311392B/en not_active Expired - Fee Related
-
2012
- 2012-08-21 WO PCT/CN2012/080434 patent/WO2013026391A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062139A (en) * | 1990-11-16 | 1992-06-24 | 帝国化学工业公司 | The method for preparing phenoxyprimidine compounds |
| GB2291874A (en) * | 1994-07-28 | 1996-02-07 | Zeneca Ltd | Etherification process |
| CN101522639A (en) * | 2006-10-09 | 2009-09-02 | 先正达有限公司 | Preparation of azoxystrobin |
Non-Patent Citations (1)
| Title |
|---|
| 董捷等: "嘧菌酯的合成", 《精细化工中间体》 * |
Cited By (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013026391A1 (en) * | 2011-08-24 | 2013-02-28 | 重庆紫光化工股份有限公司 | Synthesis method of azoxystrobin and exclusive intermediate in the synthesis thereof |
| US9556128B2 (en) | 2013-03-20 | 2017-01-31 | Nutrichem Company Limited | Preparation method for acrylate compound |
| WO2014146581A1 (en) * | 2013-03-20 | 2014-09-25 | 北京颖泰嘉和生物科技有限公司 | Method for preparing acrylate compound |
| CN103265496A (en) * | 2013-05-16 | 2013-08-28 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| WO2014183502A1 (en) * | 2013-05-16 | 2014-11-20 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| US9611226B2 (en) | 2013-05-16 | 2017-04-04 | Nutrichem Company Limited | Preparation method for azoxystrobin |
| US9920015B2 (en) | 2013-09-05 | 2018-03-20 | Nutrichem Company Limited | Methods for preparing azoxystrobin and intermediate thereof |
| US10253001B2 (en) | 2013-09-05 | 2019-04-09 | Nutrichem Company Limited | Method for preparing azoxystrobin and its intermediates |
| WO2015032192A1 (en) | 2013-09-05 | 2015-03-12 | 北京颖泰嘉和生物科技有限公司 | Methods for preparing azoxystrobin and intermediate thereof |
| CN103467387B (en) * | 2013-09-05 | 2016-03-16 | 北京颖泰嘉和生物科技股份有限公司 | A kind of method preparing Azoxystrobin and intermediate thereof |
| CN103467387A (en) * | 2013-09-05 | 2013-12-25 | 北京颖泰嘉和生物科技有限公司 | Method of preparing azoxystrobin and intermediate thereof |
| CN104725321B (en) * | 2013-12-20 | 2017-11-21 | 上海泰禾国际贸易有限公司 | A kind of preparation method of azoxystrobin intermediate |
| CN104725321A (en) * | 2013-12-20 | 2015-06-24 | 上海泰禾化工有限公司 | Preparation method of azoxystrobin intermediate |
| CN104230821A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230822A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230820A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN104230820B (en) * | 2014-09-16 | 2016-09-28 | 重庆紫光国际化工有限责任公司 | The synthetic method of Fluoxastrobin |
| CN104230821B (en) * | 2014-09-16 | 2016-07-06 | 重庆紫光国际化工有限责任公司 | The synthetic method of Fluoxastrobin |
| CN104230819A (en) * | 2014-09-16 | 2014-12-24 | 重庆紫光国际化工有限责任公司 | Method for synthesizing azoxystrobin |
| CN107602480A (en) * | 2017-09-07 | 2018-01-19 | 连云港立本作物科技有限公司 | The preparation method of Fluoxastrobin |
| EA036250B1 (en) * | 2017-10-31 | 2020-10-19 | Сиэйси Наньтун Кемикал Ко., Лтд | Method for preparing intermediates for preparing azoxystrobin |
| EP3476837A1 (en) | 2017-10-31 | 2019-05-01 | CAC Nantong Chemical Co., Ltd. | Method for preparing azoxystrobin intermediates |
| 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 |
| KR102061868B1 (en) | 2017-10-31 | 2020-01-02 | 씨에이씨 난통 케미컬 컴퍼니 리미티드 | Method for preparing azoxystrobin intermediates |
| TWI685488B (en) * | 2017-10-31 | 2020-02-21 | 大陸商南通泰禾化工股份有限公司 | Method for preparing intermediate of Azotomin (Azoxystyrin) |
| US10150741B1 (en) | 2017-10-31 | 2018-12-11 | Cac Nantong Chemical Co., Ltd | Method for preparing azoxystrobin intermediates |
| CN108516962A (en) * | 2018-05-21 | 2018-09-11 | 帕潘纳(北京)科技有限公司 | A kind of preparation method of azoxystrobin intermediate |
| US11952350B2 (en) | 2019-04-18 | 2024-04-09 | Upl Ltd. | Process for the preparation of fungicidally active strobilurin compounds and intermediates thereof |
| WO2020212919A1 (en) * | 2019-04-18 | 2020-10-22 | Upl Limited | Process for preparation of azoxystrobin and intermediates thereof |
| US12024492B2 (en) | 2019-04-18 | 2024-07-02 | Upl Ltd | Process for preparation of azoxystrobin and intermediates thereof |
| CN113767093A (en) * | 2019-04-18 | 2021-12-07 | Upl有限公司 | Process for the preparation of azoxystrobin and intermediates thereof |
| CN112174897B (en) * | 2020-09-18 | 2021-08-03 | 广东石油化工学院 | Preparation method of azoxystrobin intermediate |
| CN112174897A (en) * | 2020-09-18 | 2021-01-05 | 广东石油化工学院 | Preparation method of azoxystrobin intermediate |
| CN114685376A (en) * | 2020-12-28 | 2022-07-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of azoxystrobin intermediate |
| CN114685375A (en) * | 2020-12-28 | 2022-07-01 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of [2- (6-chloropyrimidine-4-oxygen) phenyl ] -3, 3-dimethoxyacrylic acid methyl ester |
| CN114685376B (en) * | 2020-12-28 | 2024-06-07 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of azoxystrobin intermediate |
| CN114957134A (en) * | 2022-05-26 | 2022-08-30 | 安徽广信农化股份有限公司 | Method for preparing azoxystrobin and intermediate thereof |
| CN116120241A (en) * | 2023-02-27 | 2023-05-16 | 江苏快达农化股份有限公司 | Method for synthesizing azoxystrobin intermediate by using composite catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102311392B (en) | 2014-01-22 |
| WO2013026391A1 (en) | 2013-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102311392B (en) | Synthetic method of azoxystrobin and special intermediate for synthesis | |
| CN112898299B (en) | Preparation method of palbociclib intermediate | |
| CN101967092A (en) | Method for synthesizing 2,6-dimethyl phenoxyacetic acid | |
| CN105669642B (en) | Preparation method of loflupridine hydrochloride | |
| CN109503513B (en) | One-pot synthesis method of febuxostat intermediate | |
| CN104628653B (en) | The method of synthesizing rosuvastatin spit of fland calcium key intermediate | |
| CN102942532A (en) | Preparation method of 1,4,7,10-tetraazadodecane | |
| CN100391955C (en) | Synthetic method for strotium renelate intermediate | |
| CN102516182B (en) | Preparation method for 4-amino-6-alkoxyl pyrimidine compounds | |
| CN114671859A (en) | Preparation method of rosuvastatin calcium and intermediate thereof | |
| CN110372724B (en) | Preparation method of levofloxacin cycloate | |
| CN111747926B (en) | Improved synthetic process method of topiramate free base | |
| CN113979888A (en) | Method for preparing N, N, N-trineovalerylated-1, 3, 5-triaminobenzene | |
| CN102659579A (en) | preparation method of p-chlorine methyl cinnamate | |
| CN111303045A (en) | Production process of 2-ethoxy-4, 6-difluoropyrimidine | |
| CN112830892A (en) | Synthesis method of pyridine-3-sulfonyl chloride | |
| CN101857566B (en) | Synthetic method of 2-hydroxypyridine compound | |
| CN111233835A (en) | Preparation and purification method of 5- (2-fluorophenyl) -1- (pyridine-3-ylsulfonyl) -1H-pyrrole-3-formaldehyde | |
| CN112250594B (en) | Method for preparing 3-acetamido-1-adamantanol | |
| CN104230825B (en) | The preparation method of Erlotinib alkali monohydrate crystal form Form I | |
| CN112745205B (en) | Preparation method of simod intermediate | |
| CN114524802B (en) | Synthesis method of quinoline compound | |
| CN104262332A (en) | Preparation method of olmesartan medoxomil | |
| CN111592471B (en) | Method for synthesizing cephalosporin active ester intermediate through bromination reaction | |
| CN114685298B (en) | Method for synthesizing baclofen based on photocatalytic migration strategy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Patent director of Chongqing Ziguang Chemical Co., Ltd Document name: payment instructions |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Chongqing Ziguang Chemical Co.,Ltd. The person in charge Document name: Notice of termination of patent right |
|
| DD01 | Delivery of document by public notice | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140122 Termination date: 20200824 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |